CN1098876C - Long carbon chain amide copolymer and its preparation - Google Patents
Long carbon chain amide copolymer and its preparation Download PDFInfo
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- CN1098876C CN1098876C CN99116889A CN99116889A CN1098876C CN 1098876 C CN1098876 C CN 1098876C CN 99116889 A CN99116889 A CN 99116889A CN 99116889 A CN99116889 A CN 99116889A CN 1098876 C CN1098876 C CN 1098876C
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- carbon chain
- long carbon
- bay
- diamines
- amide copolymer
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Abstract
The present invention relates to long carbon chain copolyamide, and the general formula of the repeating unit structure of the copolyamide is R3-[-HN-R1-NH-CO-R2-CO-]-nR4, n=50 to 70. Decamethylene diamine, lauryldiamine, and sebacic acid or lauric diacid react in solvents at the temperature of 60 to 80 DEG C to generate amic acid salt which is processed later through polycondensation and dehydration reaction for 10 hours at the pressure of 230 to 270 DEG C/1.3 to 1.5MPa so as to obtain the long carbon chain copolyamide, wherein the relative viscosity thereof is 1.97, and the melting point temperature is 188 to 192 DEG C. Samples molded through injection molding have the following properties: the water absorption rate is 0.11%, the notch impact strength is 34.7 kJ/m<2>, the volume resistivity is 1.58*10<13>omega. m, the surface resistivity is 1.55*10<13>omega, the specific inductive capacity is 1MHz 1.4, and the dielectric loss tangent is 8.7*10<-4>. The properties of other polyamide can not be compared with the good typical properties.
Description
Involved in the present invention is a kind of long carbon chain amide copolymer and preparation method thereof, in more detail, the present invention relates to terpolyamide of decamethylene diamine, bay diamines and sebacic acid or bay diacid and preparation method thereof.
The automotive industry of China is the mainstay industry of the national economic development, from the eighties development at full speed is just arranged, and nineteen ninety, China produced 560,000 in all kinds of automobiles, estimates 1,700,000 of productions in 2000.China's polyamide plastics was used for about 2000 tons of automotive industry in 1991, estimated to reach 7600 tons in 2000.Because polymeric amide 12 relative densities are little, water-intake rate is low, and flexible good, fusing point is low, easily processing, product size good stability.Heat decomposition temperature＞350 ℃ can heat-resisting continuously 90～120 ℃, and are low temperature resistant to-70 ℃, belong to self-extinguishing.Oil resistant, chemical-resistant resistance, electrical property might as well.Its plastics have been used for oil-pressure pipe, flexible pipe, junctor, brake hose and clutch tube, fuel tank, the fuel tube of automobile etc., and consumption is increasing recently.(below be abbreviated as PA12) still is in the lab scale stage because the polymeric amide 12 of China, so supply falls short of demand.
The preparation of the preparation of PA12 and polyamide 6 (below be abbreviated as PA6) is similar, and laurolactam becomes PA12 in 260～270 ℃ of ring-opening polymerizations in the presence of catalyzer phosphorous acid, co-catalyst oxalic acid, conditioning agent hexanolactam.In post-polymerization treatment, need not wash steps such as removing monomer with water.Should polymerization process simple, operation easily.The development what reason holds it back on earth? problem is many, the operational difficulty of laurolactam process steps, making initial feed with divinyl needs to become cyclododecatriene through trimerization, again through hydrogenation, oxidation, be dehydrogenated to cyclododecanone, cyclododecanone oxime changes into ketoxime, changes into laurolactam via the Beckman molecular transposition.
The objective of the invention is to prepare the good long carbon chain amide copolymer of a kind of physical and mechanical properties with commercially available sebacic acid or bay diacid and decamethylene diamine and the polycondensation of a spot of bay diamines, this copolyamide use temperature is near PA12, stretching and flexural strength and PA12 are equally matched, but are far superior to polyamide 1010 (below be abbreviated as PA1010), PA12 in electrical property, water-absorbent and notched Izod impact strength.Satisfy the growing needs of automotive industry with this multipolymer, also provide reliable product simultaneously for electric and electronic industry.
The repeat unit structure general formula of long carbon chain amide copolymer of the present invention is:
, it is characterized in that: in the formula: R
1=(CH
2)
10Or (CH
2)
12Methylene radical,
R
2=(CH
2)
8Or (CH
2)
10Methylene radical,
The integer of n=50～70,
R
3=-H or-NH-R
2-COOH,
R
4=-OH or-NH-R
1-NH
2
This long carbon chain amide copolymer is to generate acid amides hydrochlorate [H in 60～80 ℃ of reactions by decamethylene diamine, bay diamines and sebacic acid or bay diacid in isopropanol solvent
3 +NR
1-NH
3 +O-OC-R
2-COO
-].Then, this amido acid salt monomer in 230～270 ℃ under 1.3～1.5MPa pressure polycondensation dehydration made long carbon chain amide copolymer in 10 hours, its relative viscosity is 1.97,188～192 ℃ of fusing points.
The batching mol ratio of preparation long carbon chain amide copolymer is a diamine: diprotic acid=1: 1, and the bay diamines accounts for 0.01～3 mole of % of diamines total amount in diamine, and ratio is 0.1～2.5 mole of % preferably.Certainly, the ratio of diamine and diprotic acid, diamine is excessive ten thousand/to 2/10000ths also harmless.
Long its relative viscosity of carbochain terpolyamide according to prescription of the present invention and operating process and controlled variable preparation is 1.97,188～192 ℃ of fusing points.Long carbon chain amide copolymer can be used injection moulding, extrusion moulding processing plastic exemplar, 220～250 ℃ of processing temperature scopes, model temperature is controlled at 60～80 ℃, 120～150 ℃/1.3kPa of predrying temperature, the control moisture content is below 0.1%, injection pressure 60～120MPa, extrusion pressure 50～100MPa.The test result of master body is: water-absorbent: be immersed in the water after 24 hours 0.11%, heat-drawn wire
(0.45MPa): 161 ℃, notched Izod impact strength: 30～34.7kJ/m
2, specific inductivity
(1MHZ): 1.4, surface resistivity: 1.55 * 10
13, volume specific resistance: 1.58 * 10
13Ω m, dielectric loss angle tangent: 8.7 * 10
-4These performance index are that PA1010, PA12 are incomparable.In order to compare more intuitively, special physical and mechanical properties tabulation 1 expression with long carbon chain amide copolymer (below be abbreviated as PDDA), PA12, PA1010.
The physical and mechanical properties of the long carbochain polymeric amide of table 1
Implement best way of the present invention, now specify it for embodiment.
Embodiment 1:
1050g (6.10mol) decamethylene diamine, 21.5g (0.11mol) bay diamines and 1427.7g (6.21mol) bay two acid mixtures generate the acid amides hydrochlorate in 75 ℃ of reactions in isopropanol solvent.This salt is added in 7 liters of autoclaves,, temperature is risen to 260 ℃, under 1.4MPa pressure, react 10h, produce long carbon chain amide copolymer internal heating to 220 ℃ venting in 1.5 hours.Injection exemplar test result is a relative viscosity 1.97,188～192 ℃ of fusing points, and notched Izod impact strength is 34.85kJ/m
2
Embodiment 2:
Removing change decamethylene diamine and bay diamines consumption is decamethylene diamine 1067g (6.204mol), and outside the bay diamines 0.24g (0.0062mol), other still is 1427.7g (6.21mol) as the bay diacid, and operating process is the same with embodiment 1 with controlled variable.Injection exemplar test result: relative viscosity is 1.90,188～190 ℃ of fusing points, and notched Izod impact strength is 30kJ/m
2
Embodiment 3:
With embodiment 2 the same decamethylene diamine and the bay diamines consumptions of changing, other does not change.Promptly removing charging capacity is: decamethylene diamine 1042g (6.06mol), outside the bay diamines 30g (0.15mol), other operating process is the same with embodiment 1 with controlled variable.Injection exemplar test result is that relative viscosity is 2.04,189～191 ℃ of fusing points, notched Izod impact strength 35.8kJ/m
2
Embodiment 4:
Removing change decamethylene diamine and bay diamines consumption is decamethylene diamine 1068 grams (6.209 moles), and outside bay diamines 0.124 gram (0.00062 mole), other still is 1427.7 grams (6.21 moles) as the bay diacid, and operating process and controlled variable are with embodiment 1.The injection exemplar that obtains after tested, the result is: relative viscosity is 1.90, fusing point is 188～192, notched Izod impact strength is 30kJ/m
2
Embodiment 5:
Removing change decamethylene diamine and bay diamines consumption is decamethylene diamine 1036 grams (6.024 moles), and outside bay diamines 37.2 grams (0.186 mole), other still is 1427.7 grams (6.21 moles) as the bay diacid, and operating process and controlled variable are with embodiment 1.The injection exemplar that obtains after tested, the result is: relative viscosity is 1.97, fusing point is 189～191 ℃, notched Izod impact strength is 34.90kJ/m
2
Embodiment 6 and embodiment 7:
Embodiment 6 is the 1.3MPa except that the control reaction pressure, and other prescription, operating process and parameter are the same with embodiment 1.Injection exemplar test result: relative viscosity is 1.92,188～190 ℃ of fusing points, notched Izod impact strength 32kJ/m
2
Embodiment 7 is the 1.5MPa except that the control reaction pressure, and other prescription, operating process and parameter are the same with embodiment 1.Injection exemplar test result: relative viscosity 1.98,188～190 ℃ of fusing points, notched Izod impact strength 33kJ/m
2
Embodiment 8:
Except that 235 ℃ of control reaction temperature controls, other prescription, operating process and parameter are the same with embodiment 1.Injection exemplar test result: relative viscosity is 1.92,188～190 ℃ of fusing points, notched Izod impact strength 30kJ/m
2
Embodiment 9:
Except that 268 ℃ of control reaction temperature controls, other prescription, operating process and parameter are the same with embodiment 1.Injection exemplar test result: relative viscosity 1.99,188～190 ℃ of fusing points, notched Izod impact strength is 35kJ/m
2
Claims (2)
1, a kind of preparation method of following repeat unit structure general formula long carbon chain amide copolymer, its repeat unit structure general formula is:
In the formula: R
1Expression (CH
2)
10Or (CH
2)
12Methylene radical,
R
2Expression (CH
2)
10Methylene radical,
N=50～70 integers,
R
3Expression-H or-NH-R
2-COOH,
R
4Expression-OH or-NH-R
1-NH
2,
It is characterized in that: decamethylene diamine, bay diamines and bay diacid generate acid amides hydrochlorate [H in 60～80 ℃ in isopropanol solvent
3 +N-R
1-NH
3 +O-OC-R
2-COO
-], diamine: the mol ratio of diprotic acid equals 1: 1, and wherein the bay diamines accounts for 0.01～3 mole of % of diamines total amount, and then, the amido acid salt monomer is in 230～270 ℃, and under 1.3～1.5Mpa pressure, polycondensation dehydration 10 hours makes long carbon chain amide copolymer.
2, the preparation method of long carbon chain amide copolymer according to claim 1 is characterized in that: described bay diamines accounts for 0.1～2.5 mole of % of diamines total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116889A CN1098876C (en) | 1999-09-21 | 1999-09-21 | Long carbon chain amide copolymer and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116889A CN1098876C (en) | 1999-09-21 | 1999-09-21 | Long carbon chain amide copolymer and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1288905A CN1288905A (en) | 2001-03-28 |
| CN1098876C true CN1098876C (en) | 2003-01-15 |
Family
ID=5279558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99116889A Expired - Fee Related CN1098876C (en) | 1999-09-21 | 1999-09-21 | Long carbon chain amide copolymer and its preparation |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952786B (en) * | 2014-04-25 | 2016-05-11 | 中国科学院化学研究所 | A kind of Long Carbon Chain Polyamide fiber with controlled hydrophobic, super-hydrophobicity and its production and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904718A (en) * | 1987-07-01 | 1990-02-27 | Huels Aktiengesellschaft | Thermoplastic molding compounds which have impact strength when cold |
| US4959403A (en) * | 1988-01-28 | 1990-09-25 | Huels Aktiengesellschaft | Thermoplastic molding compositions with cold impact strength |
| US5258513A (en) * | 1991-07-25 | 1993-11-02 | Ucb S.A. | Substituted cyclopropylamino-1,3,5-triazines |
-
1999
- 1999-09-21 CN CN99116889A patent/CN1098876C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904718A (en) * | 1987-07-01 | 1990-02-27 | Huels Aktiengesellschaft | Thermoplastic molding compounds which have impact strength when cold |
| US4959403A (en) * | 1988-01-28 | 1990-09-25 | Huels Aktiengesellschaft | Thermoplastic molding compositions with cold impact strength |
| US5258513A (en) * | 1991-07-25 | 1993-11-02 | Ucb S.A. | Substituted cyclopropylamino-1,3,5-triazines |
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| Publication number | Publication date |
|---|---|
| CN1288905A (en) | 2001-03-28 |
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