Patents
Search within
Search within the title, abstract, claims, or full patent document: You can restrict your search to a specific field using field names.
Use TI= to search in the title, AB= for the abstract, CL= for the claims, or TAC= for all three. For example, TI=(safety belt).
Search by Cooperative Patent Classifications (CPCs): These are commonly used to represent ideas in place of keywords, and can also be entered in a search term box. If you're searching forseat belts, you could also search for B60R22/00 to retrieve documents that mention safety belts or body harnesses. CPC=B60R22 will match documents with exactly this CPC, CPC=B60R22/low matches documents with this CPC or a child classification of this CPC.
Learn More
Title
Abstract
Claims
Full Document
Find patents
Keywords and boolean syntax (USPTO or EPO format): seat belt searches these two words, or their plurals and close synonyms. "seat belt" searches this exact phrase, in order. -seat -belt searches for documents not containing either word.
For searches using boolean logic, the default operator is AND with left associativity. Note: this means safety OR seat belt is searched as (safety OR seat) AND belt. Each word automatically includes plurals and close synonyms. Adjacent words that are implicitly ANDed together, such as (safety belt), are treated as a phrase when generating synonyms.
Learn More
Search by
Chemistry searches match terms (trade names, IUPAC names, etc. extracted from the entire document, and processed from .MOL files.)
Substructure (use SSS=) and similarity (use ~) searches are limited to one per search at the top-level AND condition. Exact searches can be used multiple times throughout the search query.
Searching by SMILES or InChi key requires no special syntax. To search by SMARTS, use SMARTS=.
To search for multiple molecules, select "Batch" in the "Type" menu. Enter multiple molecules separated by whitespace or by comma.
Learn More
Patent numbers
Search specific patents by importing a CSV or list of patent publication or application numbers.
Long carbon chain amide copolymer and its preparation
CN1098876C
China
Worldwide applications
1999
CN
Application CN99116889A events
1999-09-21
2001-03-28
2003-01-15
Application granted
2003-01-15
2019-09-21
Anticipated expiration
Status
Expired - Fee Related
Description
translated from
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)
Hide Dependent
translated from
Claims (2)
Hide Dependent
translated from
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.