CN112029090A - High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof - Google Patents
High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof Download PDFInfo
- Publication number
- CN112029090A CN112029090A CN201910474696.4A CN201910474696A CN112029090A CN 112029090 A CN112029090 A CN 112029090A CN 201910474696 A CN201910474696 A CN 201910474696A CN 112029090 A CN112029090 A CN 112029090A
- Authority
- CN
- China
- Prior art keywords
- acid
- gas
- pa5xt
- polyamide copolymer
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 133
- 229920002647 polyamide Polymers 0.000 title claims abstract description 133
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 71
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000004677 Nylon Substances 0.000 claims description 53
- 229920001778 nylon Polymers 0.000 claims description 53
- 239000012266 salt solution Substances 0.000 claims description 46
- 238000012360 testing method Methods 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 38
- 239000012760 heat stabilizer Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 23
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 23
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 claims description 16
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 claims description 16
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 16
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 16
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 4
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 4
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 4
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 4
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 4
- 150000003503 terephthalic acid derivatives Chemical class 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 4
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000000071 blow moulding Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 238000002074 melt spinning Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a high-temperature-resistant low-water-absorption polyamide copolymer PA5XT and a preparation method thereof. The polyamide copolymer PA5XT comprises the following structural units:
and/or
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-temperature-resistant low-water-absorption polyamide copolymer PA5XT and a preparation method thereof.
Background
Polyamides are widely used for automobile parts, parts of electric and electronic equipment, and many other applications because of their excellent mechanical properties and moldability. However, the main component of polyamide nylon is polyamide, which contains amino and carbonyl groups and is easy to form hydrogen bonds with water molecules, so that various obtained materials are easy to absorb water during use, and generate a plasticizing effect, so that the volume expansion and modulus of the materials are reduced, obvious creep deformation occurs under the action of stress, and the dimensional stability is greatly reduced.
The polyamide PA6 and the polyamide PA66 are the most commonly used polyamide materials, can absorb 10 percent of moisture from humid air at the highest, and can absorb 2 to 4 percent of moisture in mass fraction under a general humidity environment, so that various mechanical property changes and dimensional deformation are caused. Therefore, it is necessary to reduce the water absorption of polyamide.
Meanwhile, the polyamide is popularized and applied in various fields due to the characteristics of stable performance, weather resistance, corrosion resistance and the like, but the polyamide needs to be further improved in heat resistance in special use environments such as the field of automobile engines.
The pentanediamine is polyamide PA56 synthesized by the monomer and a copolymer, and has excellent service performance like polyamide PA66, wherein the pentanediamine is the monomer prepared by the national proprietary intellectual property bio-based method.
In the prior art, no relevant report is provided for a polyamide copolymer PA5XT which is prepared by taking pentanediamine, long carbon chain dibasic acid and terephthalic acid as raw materials and has high temperature resistance and low water absorption performance.
Disclosure of Invention
In order to solve the defects of the prior art and products, the invention provides a polyamide copolymer PA5XT, a preparation method and application thereof.
The invention provides a polyamide copolymer PA5XT, wherein the polyamide copolymer PA5XT comprises the following structural units:
wherein x is an integer of 6 to 18, and y is an integer of 2 to 16; preferably, x is an integer of 8 to 18 and y is an integer of 4 to 8, and more preferably, x is an integer of 11 to 18 and y is an integer of 4 to 6.
The inventors have found that a suitable range of the molar ratio of the structural units (I) and (II) has a significant influence on the physico-chemical properties of the polyamide copolymer PA5 XT. In a preferred embodiment of the invention, the molar ratio of the structural units (I) and (II) in the polyesteramide is 10 to 50: 20 to 90, more preferably 10 to 50: 50-90, more preferably 15-50: 50-85.
In some preferred embodiments of the present invention, the starting material for the polyamide copolymer PA5XT comprises the following monomers:
100 parts of pentamethylene diamine, namely 100 parts of pentamethylene diamine,
5-65 parts of long-carbon-chain dibasic acid, and more preferably 10-50 parts;
5-90 parts of terephthalic acid and/or derivatives thereof, and more preferably 20-90 parts;
wherein all parts are calculated on the basis of the amount of the substance.
In some preferred embodiments of the present invention, the pentanediamine may be chemically or biologically derived, preferably biologically derived 1, 5-pentanediamine; and/or the presence of a gas in the gas,
the long carbon chain dibasic acid is selected from one or more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid, and is preferably dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid; and/or the presence of a gas in the gas,
the terephthalic acid derivative is one selected from terephthalic acid chloride, dimethyl terephthalate and diethyl terephthalate.
In some preferred embodiments of the present invention, the polyamide copolymer PA5XT further comprises 0.001 to 0.3 part, more preferably 0.01 to 0.3 part, of a heat stabilizer, wherein the parts are mole parts,
the heat stabilizer is one or more selected from phosphoric acid, phosphorous acid, trimethyl phosphite, triphenyl phosphite, trimethyl phosphate, triphenyl phosphate, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite and potassium hypophosphite.
In some preferred embodiments of the invention, the sum of the moles of the long carbon chain diacid and the moles of terephthalic acid and/or its derivatives, and the ratio of the moles of pentanediamine, is (1-1.05): 1.
in some preferred embodiments of the present invention, the mole fraction of the pentanediamine, the long carbon chain dibasic acid and the terephthalic acid and/or the derivative thereof is 100: (10-50): (20-90), more preferably 100: (10-50): (50-90), more preferably 100: (15-50): (50-85).
In some preferred embodiments of the present invention, the polyamide copolymer PA5XT has a relative viscosity of 1.0 to 3.2.
In some preferred embodiments of the invention, the ratio according to ISO-62: according to a 2008 standard test, the water absorption rate of the polyamide copolymer PA5XT is 4.0-12.1%, preferably 4.5-10%, and more preferably 5-7%.
The polyamide copolymer PA5XT has a tensile strength of 50 to 140MPa, and more preferably 60 to 120 MPa.
In some preferred embodiments of the present invention, the flexural strength of the polyamide copolymer PA5XT is 67 to 120MPa, and more preferably 79 to 120 MPa.
In some preferred embodiments of the present invention, the polyamide copolymer PA5XT has a heat distortion temperature of 140 to 260 ℃, more preferably 200 to 245 ℃.
The inventor finds out through a great deal of research that: the polyamide copolymer PA5XT utilizes rigid benzene rings contained in terephthalic acid residues to improve the heat resistance and mechanical properties of PA5 XT. Meanwhile, the steric effect generated by the benzene ring can effectively reduce the damage of water molecules to hydrogen bonds among polyamide molecules under the humidity condition, thereby reducing the combination of the water molecules and carbonyl and amino in the polyamide, namely reducing the water absorption rate and simultaneously keeping better dimensional stability. The polyamide copolymer PA5XT maintains the excellent use performance of polyamide, and simultaneously further improves the heat resistance and mechanical property. Meanwhile, a flexible alkane chain segment is introduced into the polyamide copolymer PA5XT by adopting the residue of the long carbon chain dibasic acid, so that the impact resistance of the polymer is favorably improved, the density of the amide group which is easy to absorb water in the polymer structure is reduced, and the water absorption is further reduced.
In another aspect of the present invention, a method for preparing the high temperature resistant and low water absorption polyamide copolymer PA5XT is provided, the method comprising the following steps:
1) adding pentanediamine, long carbon chain dibasic acid, terephthalic acid and/or derivatives thereof into water under an inert gas atmosphere to prepare a solution of nylon salt PA5 XT;
2) heating a solution of nylon salt PA5XT to increase the pressure in a reaction system to 0.3-3.2 Mpa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 232-270 ℃ when the pressure maintaining is finished, then reducing the pressure to reduce the pressure in the reaction system to 0-0.2 Mpa (gauge pressure), and the temperature of the reaction system is 230-300 ℃ after the pressure reduction is finished; vacuumizing to ensure that the vacuum degree is between-0.02 MPa and-0.1 MPa, and vacuumizing for 20-60 min to obtain a melt;
3) and (3) carrying out bracing and dicing on the melt to obtain the high-temperature-resistant low-water-absorption polyamide PA5XT copolymer.
In some preferred embodiments of the present invention, in step 1), the pentamethylene diamine is chemically or biologically derived, preferably biologically derived 1, 5-pentamethylene diamine; and/or the presence of a gas in the gas,
the long carbon chain dibasic acid is selected from one or more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid, and is preferably dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid; and/or the presence of a gas in the gas,
the terephthalic acid derivative is one selected from terephthalic acid chloride, dimethyl terephthalate and diethyl terephthalate.
In some preferred embodiments of the present invention, in step 1), the sum of the moles of the long carbon chain dibasic acid and terephthalic acid and/or derivative thereof, and the ratio of the moles of pentanediamine, is (1-1.05): 1.
in some preferred embodiments of the present invention, in step 1), the mole fraction of the pentanediamine, the long carbon chain dibasic acid and the terephthalic acid and/or the derivative thereof is preferably 100: (10-50): (20-90), more preferably 100: (10-50): (50-90).
In some preferred embodiments of the present invention, in step 1), the raw material of the polyamide copolymer PA5XT further includes 0.001 to 0.3 part, more preferably 0.01 to 0.3 part, of a heat stabilizer, where the parts are mole parts;
the heat stabilizer is one or more selected from phosphoric acid, phosphorous acid, trimethyl phosphite, triphenyl phosphite, trimethyl phosphate, triphenyl phosphate, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite and potassium hypophosphite.
Preferably, in step 2), the heat stabilizer is added before the salt solution is heated.
In a preferred embodiment, in the step 1), the concentration of the solution of the nylon salt PA5XT is between 40 and 75%, and the percentage is the mass percentage of the solution of the nylon salt PA5 XT.
In a preferred embodiment, in step 1), the pH value of the solution of nylon salt PA5XT at a concentration of 10% is 6 or more, preferably 7.0 to 8.2, and the percentage is a mass percentage of the solution of nylon salt PA5 XT.
In a preferred embodiment, in step 1), the inert gas includes one or more of nitrogen, argon or helium.
In a preferred embodiment, in the step 2), the heating time is within 1-2 h; and/or the presence of a gas in the gas,
the pressure for pressure maintaining is 0.3-3.2 MPa, and in the invention, as the polyamide copolymer PA5XT with better mechanical property, dimensional stability and lower water absorption rate is obtained, compared with the low pressure maintaining process (0.3-1.6 MPa) of common polymerization, the high pressure maintaining process (1.8-3.2 MPa) contains more water in a polymerization reaction system and has a certain slow polymerization effect, and the heat transfer of the system is more sufficient due to the presence of the water, so that the polymerization is more uniform, the mechanical property and the water absorption property of the polyamide copolymer PA5XT are improved, and the pressure for pressure maintaining is further preferably 1.6-3.2 MPa; and/or the presence of a gas in the gas,
the pressure maintaining time is 2-5 h; and/or the presence of a gas in the gas,
the pressure reduction time is 40 min-2 h.
In a preferred embodiment, in step 3), the relative viscosity of the polyamide copolymer PA5XT is 1.0 to 3.2.
In another aspect of the present invention, there is provided a molded article prepared from the above polyamide copolymer PA5XT as a raw material.
In order to obtain the molded article of the present invention, the polyamide copolymer PA5XT of the present invention can be molded by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, and film molding. These molded articles can be molded into a desired shape and used for resin molded articles such as automobile parts and machine parts. Compared with the prior art, the implementation of the invention has at least the following advantages:
1. the polyamide copolymer PA5XT synthesized by the invention has the same comprehensive use performance as polyamide, and uses the monomer pentamethylene diamine developed by domestic independent intellectual property rights, thereby avoiding the use of foreign monopoly monomer hexamethylene diamine.
2. The polyamide copolymer PA5XT synthesized by the invention has excellent mechanical properties, and the tensile property, the bending resistance and the impact resistance of the polyamide copolymer PA5XT are all inferior to polyamide products such as polyamide PA6, polyamide PA66 and the like used in the market.
3. The polyamide copolymer PA5XT synthesized by the method has lower water absorption, better dimensional stability and higher thermal deformation temperature than polyamide PA6 and polyamide PA66, can be used in a more severe use environment, and expands the use range of polyamide to a certain extent.
4. The preparation method of the polyamide copolymer PA5XT is simple, the process parameters are easy to control, large instruments are not needed for assistance, and the quantitative production is convenient to carry out.
5. The polyamide copolymer PA5XT enriches the variety of polyamide copolymers and is a product with a novel structure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Method for detecting relative viscosity eta r
Concentrated sulfuric acid method with Ubbelohde viscometer: the dried polyamide sample was weighed accurately at 0.5. + -. 0.0002g, dissolved by adding 50mL of concentrated sulfuric acid (98%), and the concentrated sulfuric acid flow time t0 and the polyamide solution flow time t were measured and recorded in a thermostatic water bath at 25 ℃.
Relative viscosity calculation formula:
relative viscosity eta r t/t0
Wherein: t: the time of solution flow; t 0: the solvent was run through time.
Mechanical property testing method
Bending test reference standard ISO-178, test conditions: 2 mm/min;
tensile test reference standard ISO-572-2, test conditions: 50 mm/min;
water absorption test: ISO-62: 2008;
dimensional stability (shrinkage) test: ISO-2577-2007;
testing the heat distortion temperature: ASTM D648;
the impact test is a cantilever beam notch impact reference test standard ISO-180/1A, and the test conditions are as follows: at 23 ℃.
1, 5-Pentanediamine, Tridecanedioic acid, tetradecanedioic acid were purchased from Kaiser (Jinxiang) biomaterials Co., Ltd., terephthalic acid was purchased from Guinea (Shanghai) industries Co., Ltd., and adipic acid was purchased from Chemicals, Inc., of the national drug group. Other starting materials, reagents are either prepared by methods well known in the literature or are commercially available.
Example 1
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 2mol of tridecanedioic acid (DC13), 8mol of terephthalic acid (PTA) and water, wherein the molar ratio of the 1, 5-pentanediamine to the terephthalic acid to the DC13 is 1:0.8:0.2, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.98.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, maintaining the temperature at 243 deg.C for 3 hr, reducing the pressure to 0.005Mpa (gauge pressure), and increasing the temperature at 290 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, bracing and dicing to obtain the polyamide copolymer.
The relative viscosity test of the obtained polyamide copolymer PA513T gave a result of 2.71. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Example 2
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 4mol of tridecanedioic acid (DC13), 6mol of terephthalic acid (PTA) and water, wherein the molar ratio of the 1, 5-pentanediamine to the terephthalic acid to the tridecanedioic acid is 1:0.6:0.4, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.98.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, maintaining the temperature at 245 deg.C for 3 hr, reducing the pressure to 0.005Mpa (gauge pressure), and increasing the temperature at 290 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, bracing and dicing to obtain the polyamide copolymer.
The relative viscosity test of the obtained polyamide copolymer PA513T gave a result of 2.73. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Example 3
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 5mol of tridecanedioic acid (DC13), 5mol of terephthalic acid (PTA) and water, wherein the molar ratio of the 1, 5-pentanediamine to the terephthalic acid to the tridecanedioic acid is 1:0.5:0.5, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.98.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, maintaining the temperature at 245 deg.C for 3 hr, reducing the pressure to 0.005Mpa (gauge pressure), and increasing the temperature at 290 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, bracing and dicing to obtain the polyamide copolymer.
The polyamide copolymer PA513T obtained was subjected to a relative viscosity test and found to be 2.70. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Example 4
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 6mol of tridecanedioic acid (DC13), 4mol of terephthalic acid (PTA) and water, wherein the molar ratio of the 1, 5-pentanediamine, the terephthalic acid and the tridecanedioic acid is 1:0.4:0.6, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.99.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, maintaining the temperature at 245 deg.C for 3 hr, reducing the pressure to 0.005Mpa (gauge pressure), and increasing the temperature at 290 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, bracing and dicing to obtain the polyamide copolymer.
The relative viscosity test of the resulting polyamide copolymer PA513T gave a result of 2.72. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Example 5
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 4mol of tridecanedioic acid (DC13), 6mol of terephthalic acid (PTA) and water, wherein the molar ratio of the 1, 5-pentanediamine to the terephthalic acid to the tridecanedioic acid is 1:0.6:0.4, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.99.
And adding a heat stabilizer phosphorous acid into the 60 wt.% nylon salt solution, wherein the adding amount of the heat stabilizer phosphorous acid is 0.002mol and 0.02%, and the percentage is the percentage of the total acid in molar weight.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, maintaining the temperature at 245 deg.C for 3 hr, reducing the pressure to 0.005Mpa (gauge pressure), and increasing the temperature at 290 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) The melt was discharged, drawn into strands and pelletized, to obtain a polyamide copolymer which was slightly yellow in color as compared with the polyamide copolymer obtained in example 2.
The polyamide copolymer PA513T obtained was subjected to a relative viscosity test and found to be 2.70. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Example 6
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 4mol of tridecanedioic acid (DC13), 6mol of terephthalic acid (PTA) and water, wherein the molar ratio of the 1, 5-pentanediamine to the terephthalic acid to the tridecanedioic acid is 1:0.6:0.4, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.99.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 1.60Mpa, taking 1 hour and 30 minutes, exhausting, maintaining the pressure at 1.60Mpa, keeping the temperature of the reaction system at 245 ℃ when the pressure maintaining is finished, reducing the pressure to 0.005Mpa (gauge pressure) when the pressure maintaining is taken for 3 hours, reducing the temperature of the reaction system at 290 ℃ when the pressure reducing is finished, and taking 1 hour for pressure reducing.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, bracing and dicing to obtain the polyamide copolymer.
The polyamide copolymer PA513T obtained was subjected to a relative viscosity test and found to be 2.74. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Example 7
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 4mol of tetradecanedioic acid (DC14) and 6mol of terephthalic acid (PTA) with water, wherein the molar ratio of the 1, 5-pentanediamine to the terephthalic acid to the tetradecanedioic acid is 1:0.6:0.4, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.99.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, maintaining the temperature at 245 deg.C for 3 hr, reducing the pressure to 0.005Mpa (gauge pressure), and increasing the temperature at 290 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 310 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, bracing and dicing to obtain the polyamide copolymer.
The polyamide copolymer PA5XT obtained was subjected to a relative viscosity test and found to be 2.62. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Comparative example 1
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 10mol of adipic acid (DC6) and water, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1:1, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.98.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, reducing the pressure to 0.005Mpa (gauge pressure) after 3 hr, and decreasing the temperature to 275 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, drawing into strips and cutting into granules to obtain the polyamide PA56 resin.
The relative viscosity test of the obtained polyamide PA56 resin showed 2.70. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Comparative example 2
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 10mol of tridecane dibasic acid (DC13) and water, wherein the molar ratio of the 1, 5-pentanediamine to the DC13 is 1:1, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at 10 wt.% nylon salt solution concentration was 8.20.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, reducing the pressure to 0.005Mpa (gauge pressure) after 3 hr, and decreasing the temperature to 275 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And melting, discharging, drawing strips and cutting into granules to obtain the polyamide PA513 resin.
The relative viscosity of the obtained polyamide PA513 resin was measured and found to be 2.74. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Comparative example 3
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 6-hexamethylene diamine (6N), 10mol of adipic acid (DC6) and water, wherein the molar ratio of the 1, 6-hexamethylene diamine to the adipic acid is 1:1, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.98.
And adding a heat stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the addition amount of the heat stabilizer sodium hypophosphite is 0.002mol and 0.02%, and the percentage is the percentage accounting for the molar weight of the total acid.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, maintaining the pressure at 2.40Mpa for 1 hr and 30min, reducing the pressure to 0.005Mpa (gauge pressure) after 3 hr, and decreasing the temperature to 275 deg.C for 1 hr.
(3) Vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) And (4) melting, discharging, drawing into strips and cutting into granules to obtain the polyamide PA66 resin.
The relative viscosity test of the obtained polyamide PA66 resin showed 2.70. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
Comparative example 4
(1) Under the condition of nitrogen, uniformly mixing 10mol of 1, 5-pentanediamine, 4mol of adipic acid and 6mol of terephthalic acid (PTA) with water, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1:0.6:0.4, and preparing 60 wt.% of nylon salt solution, wherein the percentage is the mass percentage of the nylon salt solution; the pH at a nylon salt solution concentration of 10 wt.% was 7.98.
And adding 0.002mol, 0.02% of thermal stabilizer sodium hypophosphite into the 60 wt.% nylon salt solution, wherein the percentage is the percentage of the total acid molar weight.
(2) Heating the solution, increasing the pressure in the reaction system to 2.40Mpa, taking 1 hour and 30 minutes, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and 3 hours after the pressure maintaining is used, and taking 1 hour after the pressure reducing is finished and the temperature of the reaction system is 290 ℃;
(3) vacuumizing at-0.08 MPa for 30min at 290 deg.C to obtain polyamide copolymer melt.
(4) Melting, discharging, bracing and dicing to obtain polyamide copolymerized polyamide resin;
the obtained PA56T copolymer resin was subjected to a relative viscosity test, and the result was 2.71. Reference is then made to standard ISO-178, standard ISO-572-2, standard ISO-62: 2008. ISO-2577-2007 and ASTM D648 test the thermal performance and water absorption of the prepared transparent polyamide; the test results show that the tensile strength, flexural strength, water absorption, heat distortion temperature and measurement results of the resin are shown in Table 1.
TABLE 1
As can be seen from Table 1:
1. by comparing examples 1-4 with comparative examples 1 and 2, the addition of terephthalic acid caused a significant increase in the heat distortion temperature, tensile strength, and flexural strength of polyamide copolymer PA5 XT. The rigid benzene ring in the terephthalic acid segment is favorable for improving the rigidity and the heat resistance of a polymer chain, so that the thermodynamic property of the polyamide copolymer PA5XT is obviously improved, the restriction of the performance of the polyamide copolymer PA5X is overcome, and the polyamide copolymer with excellent comprehensive performance is obtained.
2. As can be seen by comparing examples 1-4 with comparative examples 1-3, the polyamide copolymer PA5XT in the examples of the invention has excellent comprehensive performance, higher tensile strength, bending strength, impact strength, lower water absorption and dimensional stability compared with polyamide PA513, polyamide PA66 and polyamide PA 56. Compared with the polyamide copolymer PA56T with the medium-long carbon chain segment, the polyamide copolymer PA5XT with the long carbon chain segment has the advantages of low water absorption, good dimensional stability, high impact strength and the like, and has very excellent performance advantages in a certain application field.
In conclusion, the polyamide copolymer PA5XT synthesized by the invention has a novel structural composition and performance superior to that of polyamide synthesized by conventional monomers, and can be used in resin molded products of automobile parts, mechanical parts and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Polyamide copolymer PA5XT, characterized in that the polyamide copolymer PA5XT comprises the following structural units:
and/or
Wherein x is an integer of 6 to 18, and y is an integer of 2 to 16; preferably, x is an integer of 8 to 18 and y is an integer of 4 to 8, and more preferably, x is an integer of 11 to 18 and y is an integer of 4 to 6.
2. Polyamide copolymer PA5XT, characterized in that the polyamide copolymer PA5XT is prepared from the following monomers:
100 parts of pentamethylene diamine, namely 100 parts of pentamethylene diamine,
5-65 parts of long-carbon-chain dibasic acid, and more preferably 10-50 parts;
5-90 parts of terephthalic acid and/or derivatives thereof, and more preferably 20-90 parts;
wherein all parts are by weight of the material;
the long carbon chain dibasic acid is selected from one or more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid, and is preferably dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid.
3. Polyamide copolymer PA5XT according to claim 2, characterized in that the pentanediamine is of chemical or biological origin, preferably 1, 5-pentanediamine of biological origin; and/or the presence of a gas in the gas,
the terephthalic acid derivative is one of terephthalic acid chloride, dimethyl terephthalate and diethyl terephthalate; and/or the presence of a gas in the gas,
the sum of the mole numbers of the long carbon chain dibasic acid and the terephthalic acid and/or the derivative thereof and the mole number ratio of the pentanediamine are (1-1.05): 1; and/or the presence of a gas in the gas,
the mole fraction of the pentanediamine, the long carbon chain dibasic acid and the terephthalic acid and/or the derivative thereof is preferably 100: (10-50): (20-90), more preferably 100: (10-50): (50-90).
4. The polyamide copolymer PA5XT of claim 2, wherein the polyamide copolymer PA5XT further comprises 0.001-0.3 part, preferably 0.01-0.3 part, of a heat stabilizer, the parts being mole parts,
the heat stabilizer is one or more selected from phosphoric acid, phosphorous acid, trimethyl phosphite, triphenyl phosphite, trimethyl phosphate, triphenyl phosphate, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite and potassium hypophosphite.
5. The polyamide copolymer PA5XT of claim 2, wherein the polyamide copolymer PA5XT has a relative viscosity of 1.0 to 3.2; and/or the presence of a gas in the gas,
according to ISO-62: according to a 2008 standard test, the water absorption rate of the polyamide copolymer PA5XT is 4.0-12.1%, preferably 4.5-10%, and more preferably 5-7%; and/or the presence of a gas in the gas,
the polyamide copolymer PA5XT has a tensile strength of 50-140 MPa, and more preferably 60-120 MPa; and/or the presence of a gas in the gas,
the bending strength of the polyamide copolymer PA5XT is 67-120 MPa, and preferably 79-120 MPa; and/or the presence of a gas in the gas,
the polyamide copolymer PA5XT has a heat distortion temperature of 140-260 ℃, and more preferably 200-245 ℃.
6. A process for preparing the polyamide copolymer PA5XT as claimed in any one of claims 1 to 5, characterized in that it comprises the following steps:
1) under the inert gas atmosphere, adding pentanediamine, long carbon chain dibasic acid, terephthalic acid and/or derivatives thereof into water to prepare a solution of nylon salt PA5 XT;
2) heating a solution of nylon salt PA5XT to increase the pressure in a reaction system to 0.3-3.2 Mpa, exhausting and maintaining the pressure, wherein the temperature of the reaction system is 232-270 ℃ when the pressure maintaining is finished, then reducing the pressure to reduce the pressure in the reaction system to 0-0.2 Mpa (gauge pressure), and the temperature of the reaction system is 230-300 ℃ after the pressure reduction is finished; vacuumizing to ensure that the vacuum degree is between-0.02 MPa and-0.1 MPa, and vacuumizing for 20-60 min to obtain a melt;
3) carrying out bracing and dicing on the melt to obtain the high-temperature-resistant low-water-absorption polyamide PA5XT copolymer;
wherein, the long carbon chain dibasic acid is selected from one or more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid, and is preferably dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid.
7. The process according to claim 6, characterized in that in step 1), the pentanediamine is of chemical or biological origin, preferably 1, 5-pentanediamine of biological origin; and/or the presence of a gas in the gas,
the terephthalic acid derivative is one selected from terephthalic acid chloride, dimethyl terephthalate and diethyl terephthalate.
8. The method of claim 6, wherein, in step 1),
the sum of the mole numbers of the long carbon chain dibasic acid and the terephthalic acid and/or the derivative thereof and the mole number ratio of the pentanediamine are (1-1.05): 1; and/or the presence of a gas in the gas,
the mole fraction of the pentanediamine, the long carbon chain dibasic acid and the terephthalic acid and/or the derivative thereof is preferably 100: (10-50): (20-90), more preferably 100: (10-50): (50-90); and/or the presence of a gas in the gas,
the polyamide copolymer PA5XT also comprises 0.001-0.3 part of heat stabilizer, more preferably 0.01-0.3 part, wherein the parts are mole parts;
the heat stabilizer is one or more selected from phosphoric acid, phosphorous acid, trimethyl phosphite, triphenyl phosphite, trimethyl phosphate, triphenyl phosphate, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite and potassium hypophosphite.
9. The method of claim 6, wherein, in step 2),
adding the heat stabilizer before heating the salt solution; and/or the presence of a gas in the gas,
the pressure for maintaining the pressure is 0.3-3.2 Mpa, and the preferable pressure is 1.6-3.2 Mpa; and/or the presence of a gas in the gas,
and the pressure maintaining time is 2-5 h.
10. A molded article, which is molded by one or more molding methods selected from the group consisting of injection molding, extrusion molding, blow molding, vacuum molding, melt spinning and film molding, using the polyamide copolymer PA5XT according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910474696.4A CN112029090A (en) | 2019-06-03 | 2019-06-03 | High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910474696.4A CN112029090A (en) | 2019-06-03 | 2019-06-03 | High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112029090A true CN112029090A (en) | 2020-12-04 |
Family
ID=73575782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910474696.4A Pending CN112029090A (en) | 2019-06-03 | 2019-06-03 | High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112029090A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479440A (en) * | 2021-12-14 | 2022-05-13 | 华东理工大学 | Low-water-absorption PA56T/PET composite material and preparation method thereof |
| WO2023025282A1 (en) * | 2021-08-27 | 2023-03-02 | 上海凯赛生物技术股份有限公司 | Odd-numbered carbon polyamide elastomer and preparation method therefor |
| CN115894900A (en) * | 2021-08-05 | 2023-04-04 | 上海凯赛生物技术股份有限公司 | Polyamide copolymer PA6IT and preparation method thereof |
| CN115960348A (en) * | 2021-10-08 | 2023-04-14 | 上海凯赛生物技术股份有限公司 | Bio-based polyamide resin and preparation method thereof, polyamide industrial yarn and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378800A (en) * | 1990-12-12 | 1995-01-03 | E. I. Du Pont De Nemours And Company | Terephthalic acid copolyamides |
| CN101374884A (en) * | 2006-01-26 | 2009-02-25 | 帝斯曼知识产权资产管理有限公司 | Semi-crystalline semi-aromatic polyamides |
| JP2011111576A (en) * | 2009-11-30 | 2011-06-09 | Toyobo Co Ltd | Copolyamide |
| CN105331092A (en) * | 2014-08-07 | 2016-02-17 | 上海凯赛生物技术研发中心有限公司 | Highly wear-resistant bio-based polyamide composite material and preparation method thereof |
| CN107383365A (en) * | 2017-08-09 | 2017-11-24 | 无锡殷达尼龙有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof |
| CN109517165A (en) * | 2017-09-18 | 2019-03-26 | 上海凯赛生物技术研发中心有限公司 | A kind of semi-aromatic biological poly amide and preparation method thereof |
-
2019
- 2019-06-03 CN CN201910474696.4A patent/CN112029090A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378800A (en) * | 1990-12-12 | 1995-01-03 | E. I. Du Pont De Nemours And Company | Terephthalic acid copolyamides |
| CN101374884A (en) * | 2006-01-26 | 2009-02-25 | 帝斯曼知识产权资产管理有限公司 | Semi-crystalline semi-aromatic polyamides |
| JP2011111576A (en) * | 2009-11-30 | 2011-06-09 | Toyobo Co Ltd | Copolyamide |
| CN105331092A (en) * | 2014-08-07 | 2016-02-17 | 上海凯赛生物技术研发中心有限公司 | Highly wear-resistant bio-based polyamide composite material and preparation method thereof |
| CN107383365A (en) * | 2017-08-09 | 2017-11-24 | 无锡殷达尼龙有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof |
| CN109517165A (en) * | 2017-09-18 | 2019-03-26 | 上海凯赛生物技术研发中心有限公司 | A kind of semi-aromatic biological poly amide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 温变英等: "《高分子材料加工》", 30 June 2016 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894900A (en) * | 2021-08-05 | 2023-04-04 | 上海凯赛生物技术股份有限公司 | Polyamide copolymer PA6IT and preparation method thereof |
| WO2023025282A1 (en) * | 2021-08-27 | 2023-03-02 | 上海凯赛生物技术股份有限公司 | Odd-numbered carbon polyamide elastomer and preparation method therefor |
| CN115960348A (en) * | 2021-10-08 | 2023-04-14 | 上海凯赛生物技术股份有限公司 | Bio-based polyamide resin and preparation method thereof, polyamide industrial yarn and preparation method and application thereof |
| CN114479440A (en) * | 2021-12-14 | 2022-05-13 | 华东理工大学 | Low-water-absorption PA56T/PET composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4346691B2 (en) | Auto parts made from polyamide compositions | |
| KR0168468B1 (en) | Polyamide and polyimide compositions | |
| US4387184A (en) | Heat stable polyphase polyamide compositions and preparation thereof | |
| CN112759760B (en) | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof | |
| US5011893A (en) | Method for producing a block copolyamide | |
| US20030050376A1 (en) | Polyamide composition | |
| CN112029090A (en) | High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof | |
| CN113121817B (en) | Polyamide copolymer 56TI with low water absorption rate, and preparation method and application thereof | |
| MX2008009628A (en) | Semi-crystalline semi-aromatic polyamide | |
| CN113150269A (en) | Semi-aromatic polyamide copolymer and preparation thereof | |
| CN115093561B (en) | Wen Gaozu-resistant long-chain polyamide and preparation method thereof | |
| JPH07228776A (en) | Polyamide composition for molding material | |
| CN113214472B (en) | Low-water-absorption high-toughness polyamide copolymer 513TI and preparation method thereof | |
| EP2726537A1 (en) | Branched polyamide with different blocks | |
| KR101969176B1 (en) | Semi-aromatic polyamide | |
| CN115612095A (en) | A kind of high temperature resistant semi-aromatic copolyamide and its preparation method, composition and molded article | |
| JP2022100975A (en) | Polyamide composition and molded body | |
| KR101570562B1 (en) | Polyamide resin, method for preparing the same, and article comprising the same | |
| JP2019182930A (en) | Transparent polyamide, transparent polyamide composition and transparent polyamide compact | |
| US4212965A (en) | Polyamides with elastomeric character from 5-methylnonamethylene diamine | |
| JP2018044103A (en) | Transparent polyamide and transparent polyamide molded body | |
| JP3523316B2 (en) | Production method of semi-aromatic polyamide | |
| JPH07228695A (en) | New polyamide manufacturing method | |
| JP2952930B2 (en) | Polyarylene sulfide resin composition | |
| JPH0424386B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |