CN110172146A - A kind of preparation method of high-performance heat resistant polyamide - Google Patents
A kind of preparation method of high-performance heat resistant polyamide Download PDFInfo
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- CN110172146A CN110172146A CN201910467134.7A CN201910467134A CN110172146A CN 110172146 A CN110172146 A CN 110172146A CN 201910467134 A CN201910467134 A CN 201910467134A CN 110172146 A CN110172146 A CN 110172146A
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- acid
- diamines
- heat resistant
- kettle
- resistant polyamide
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- 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
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- 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
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- 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 present invention relates to a kind of polyamide, and in particular to a kind of preparation method of high-performance heat resistant polyamide, the polyamide are that following components is copolymerized: the structural unit of the methyl cyclohexane diamines HTDA and terephthalic acid (TPA) PTA of (A) 60-90wt%；(B) structural unit of the methyl cyclohexane diamines HTDA of at least 10wt% and other a kind of and terephthalic acid (TPA) PTA different aliphatic or aromatic dicarboxylic acid, either a kind of and methyl cyclohexane diamines HTDA different other aliphatic or aromatic diamine and the structural unit of a kind of and terephthalic acid (TPA) PTA different other aliphatic or aromatic dicarboxylic acid, wherein the dicarboxylic acids is aliphatic or aromatic dicarboxylic acid with 4-36 carbon atom, and the diamines is aliphatic or aromatic diamine with 4-22 carbon atom；(C) additive of 1wt%, including the antioxidant of 0.002-0.01wt%.
Description
Technical field
The present invention relates to a kind of polyamide, and in particular to a kind of preparation method of high-performance heat resistant polyamide.
Background technique
Nylon is constantly made its high-performance by physics and chemical modification as current important engineering plastics
Change, so that nylon maintains the leading position in fierce market competition, many fields are to the high temperature resistant aspect of material and resistance to height
It is proposed new requirement in terms of the functionalization of adiabator, in order to adapt to these new demands, people are in exploitation new product high temperature resistant Buddhist nun
A large amount of effort has been done in terms of imperial pipe.
Wherein, semi-aromatic nylon (PPA) is with the diacid with aromatic rings or diamines by aliphatic diamine or diacid through contracting
Poly- obtained, these nylon materials not only improve thermal deformation temperature because having aromatic ring structure in chemical structure to some extent
Degree, also improves the rigidity and dimensional stability of material, is suitable for present new demand.Many semi-aromatic high temperature resistants at present
The PPA product such as use, such as PA4T, PA6T/66, PA6T/6I, PA9T, PA10T, PAMXD6 and PA12T has been put into nylon.
But the high temperature resistant nylon used now all haves the defects that itself.
It include especially the semi-aromatic nylon of 1,6- hexamethylene diamine and terephthalic acid (TPA) as main component, because of its raw material
It is from a wealth of sources, it is cheap, preferentially it is used more widely.But since too high (380 DEG C or so) of PA6T fusing point are so that its processing temperature
The high-temperature nylon for the PA6T series for substantially exceeding its decomposition temperature, therefore using now is all the diamines by adding another component
And/or diacid copolymerization, to obtain with the practicability product compared with the good melt-processable of low melting point.Such as US662721 is retouched
PA6T/6I copolymer is stated；CN1127266A describes PA6T/66 series copolymer；It is described in WO2007/071790-A1
PA6T/9T copolymer etc..However, being added in combination for these additional diamines and/or dicarboxylic acids, can be effectively reduced fusing point and improve
Processing performance, while other performances are reduced, it is mainly manifested in glass transition temperature and substantially reduces, rigidity reduces and size
Stability etc..
For high temperature resistant nylons such as PA9T, PA10T and PA12T.Such as PA9T high temperature resistant is described in JP2000186142A
Nylon.It is such to have excellent heat resistance, ultralow water absorption rate, better dimensional stability, but diamines used in such product former
The higher cost of material, and the glass transition temperature of product at 140 DEG C hereinafter, require product rigidity it is strong field application not
Foot.
Summary of the invention
In order to overcome the above problem, the present invention provides a kind of preparation methods of high-performance heat resistant polyamide, by drawing
Enter methyl cyclohexane diamines (abbreviation HTDA) cycloaliphatic ring special construction, reduces the crystallinity of final copolyamide, intermolecular arrangements
Variation, and then mobility is improved, while reaching identical resistance to temp effect, product of the invention has lower fusing point, into
And processing temperature is reduced, it reduces costs.
The present invention is achieved by the following technical solutions:
A kind of high-performance heat resistant polyamide, the polyamide are that following components is copolymerized:
(A) structural unit of the methyl cyclohexane diamines (abbreviation HTDA) of 60-90wt% and terephthalic acid (TPA) (abbreviation PTA)；
(B) structural unit or a kind of fat of at least HTDA of 10wt% and a kind of aliphatic/aromatic dicarboxylic acids
The structural unit of race/aromatic diamine and a kind of aliphatic/aromatic dicarboxylic acids, wherein the dicarboxylic acids is with 4-36 carbon
The aliphatic/aromatic dicarboxylic acids of atom, the diamines is the aliphatic/aromatic diamines with 4-22 carbon atom, described
Dicarboxylic acids does not include PTA, and the diamines does not include HTDA；
(C) additive of 1wt%, including the antioxidant of 0.002-0.01wt%；
Wherein, component (A)~(C) amount is total up to 100% by weight；
Wherein, component (B) diamines is one of pentanediamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, dodecamethylene diamine；
Wherein, component (B) dicarboxylic acids is adipic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid, hexamethylene two
Carboxylic acid and its mixture, pimelic acid, suberic acid, azelaic acid, heneicosanedioic acid, tridecandioic acid, tetracosandioic acid, pentadecane two
One of acid, hexadecandioic acid (hexadecane diacid), heptadecane diacid, octadecane diacid；
Wherein, component (B) dicarboxylic acids is one of adipic acid, decanedioic acid and M-phthalic acid；
Wherein, the component (C) antioxidant is one or more of phosphoric acid, phosphorous acid, hypophosphorous acid；
Wherein, the melt temperature scope of the high-performance heat resistant polyamide is 260-320 DEG C, and glass transition temperature is big
In 135 DEG C；
Wherein, the heat resistant polyamide of the high-performance heat resistant polyamide compared with the prior art, in identical fusing point, viscosity
Under molecular mass regimes, melt index improves 10-40g/10min, and processing temperature reduces at least 10 DEG C；
A kind of preparation method of high-performance heat resistant polyamide, comprising the following steps:
S1, methyl cyclohexane diamines HTDA, terephthalic acid (TPA) PTA and water are placed in the first salt dissolving tank, heat salt-forming reaction
Component (A) is obtained, HTDA or diamines, dicarboxylic acids and water are placed in the second salt dissolving tank, heating salt-forming reaction obtains component (B),
After the completion of salt, component (A), component (B) and component (C) are put into polymeric kettle；
S2, using air in carbon dioxide replacement kettle, at least twice；
S3, heating polymeric kettle open stirring until when temperature in the kettle reaches 150-170 DEG C, continue to be heated to temperature in the kettle to reach
To 220-280 DEG C, pressure 1.5-2.5MPa, heat-insulation pressure keeping is reacted；
When material solid content is 70% in S4, measurement kettle, slow pressure release, until stopping when material solid content is 80% in kettle
Heating and stirring spray prepolymer in kettle, and obtained solid product cools down under a nitrogen, obtains solid prepolymer；
S5, S4 obtained solid prepolymer is dried, puts into solid phase kettle, heats under nitrogen protection, be warming up to 220-
260 DEG C, heat-insulation pressure keeping reacts 8-12h, and discharging obtains the high-performance heat resistant polyamide.
The beneficial effects of the present invention are: the series high temperature resistant polyamides such as (1) and existing PA46, PA66, PA6T, PA9T, PA10T
Amine product is compared, and glass transition temperature is higher than the high temperature resistant nylon product now used just to be had in the case where more low melting point
Higher glass transition temperature reaches the existing resistance to temp effect using high temperature resistant nylon product；(2) have better mobility and
Processing performance reduces the crystallinity of final copolyamide by introducing methyl cyclohexane diamines cycloaliphatic ring special construction, intermolecular
Arrangement variation, and then mobility is improved, it is identical with fusing point in viscosity it has been confirmed by experiments that compared with existing heat resistant polyamide
In the case where, the product melt index of the invention can improve 10-40g/10min, and processing temperature reduces by 10 DEG C or more；(3) and now
There is high temperature resistant nylon product to compare, while reaching identical resistance to temp effect, product of the invention has lower fusing point, in turn
Reduce processing temperature.
Specific embodiment
Here is that the present invention is further described in conjunction with the embodiments.
Embodiment 1
S1,1.74kg methyl cyclohexane diamines, 2.26kg terephthalic acid (TPA) and 3kg deionized water are placed in the first salt dissolving tank
In, heating reaction obtains salt A, and 0.47kg methyl cyclohexane diamines, 0.53kg adipic acid and 1kg deionized water are placed in the second salt dissolving
In bucket, heating reaction obtains salt B.Salt A, salt B and 0.5g sodium hypophosphite are put into 50L polymeric kettle at after the completion of salt；
S2, using air in carbon dioxide replacement kettle twice；
S3, heating polymeric kettle open stirring until when temperature in the kettle reaches 150 DEG C, continue to be heated to temperature in the kettle to reach
When 230 DEG C, pressure 1.85MPa, heat-insulation pressure keeping is reacted；
When material solid content is 70% in S4, measurement kettle, slow pressure release, until (can be with when material solid content is 80% in kettle
The water that is discharged in measurement polymerization process is collected by using captation, then calculates material solid content in kettle), stop heating and
Stirring, prepolymer in kettle is sprayed, obtained solid product cools down under a nitrogen, obtains solid prepolymer；
S5, S4 obtained solid prepolymer is dried, puts into solid phase kettle, heats under nitrogen protection, be warming up to 240
DEG C, heat-insulation pressure keeping reacts 8h, and discharging obtains product PAHTDAT/HTDA6 copolymer nylon.
The fusing point of the product is 298 DEG C after tested, and glass transition temperature is up to 155 DEG C, and existing high-temperature nylon product
Under conditions of higher fusing point, it is also difficult to reach so high glass transition temperature；With identical fusing point and identical molecular weight
PA6T/6I product compare, glass transition temperature is increased to 155 DEG C by 110 DEG C, and melt index is increased to by 50g/10min
75g/10min, processing temperature are reduced to 310 DEG C by 325 DEG C.
Embodiment 2
S1,1.53kg methyl cyclohexane diamines, 1.97kg terephthalic acid (TPA) and 3kg deionized water are placed in the first salt dissolving tank
In, heating reaction obtains salt A, 0.83kg adipic acid, 0.67kg hexamethylene diamine and 1kg deionized water is placed in the second salt dissolving tank,
Heating reaction obtains salt B, puts into salt A, salt B and 0.5g sodium hypophosphite in 50L polymeric kettle at after the completion of salt；
S2, using air in carbon dioxide replacement kettle twice；
S3, heating polymeric kettle open stirring until when temperature in the kettle reaches 160 DEG C, continue to be heated to temperature in the kettle to reach
When 240 DEG C, pressure 2.0MPa, heat-insulation pressure keeping is reacted；
When material solid content is 70% in S4, measurement kettle, slow pressure release, until (can be with when material solid content is 80% in kettle
The water that is discharged in measurement polymerization process is collected by using captation, then calculates material solid content in kettle), stop heating and
Stirring, prepolymer in kettle is sprayed, obtained solid product cools down under a nitrogen, obtains solid prepolymer；
S5, S4 obtained solid prepolymer is dried, puts into solid phase kettle, heats under nitrogen protection, be warming up to 250
DEG C, heat-insulation pressure keeping reacts 9h, and discharging obtains product PAHTDAT/66 copolymer nylon.
After tested compared with the PA6T/66 of identical fusing point and identical molecular weight, glass transition temperature is increased to by 108 DEG C
145 DEG C, melt index increases to 68g/10min by 40g/10min, and processing temperature is reduced to 315 DEG C by 330 DEG C.
Claims (8)
1. a kind of high-performance heat resistant polyamide, which is characterized in that the polyamide is that following components is copolymerized:
(A) the methyl cyclohexane diamines of 60-90wt% and the structural unit of terephthalic acid (TPA)；
(B) structural unit of the methyl cyclohexane diamines of at least 10wt% and a kind of aliphatic/aromatic dicarboxylic acids, or it is a kind of
The structural unit of aliphatic/aromatic diamines and a kind of aliphatic/aromatic dicarboxylic acids, wherein the dicarboxylic acids is with 4-36
The aliphatic/aromatic dicarboxylic acids of a carbon atom, the diamines are the aliphatic/aromatic diamines with 4-22 carbon atom,
The dicarboxylic acids does not include terephthalic acid (TPA), and the diamines does not include methyl cyclohexane diamines；
(C) additive of 1wt%, including the antioxidant of 0.002-0.01wt%；
Wherein component (A)~(C) amount is total up to 100% by weight.
2. a kind of high-performance heat resistant polyamide according to claim 1, which is characterized in that component (B) diamines is penta
One of diamines, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, dodecamethylene diamine.
3. a kind of high-performance heat resistant polyamide according to claim 1, which is characterized in that component (B) described dicarboxylic acids is
Adipic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid, cyclohexane dicarboxylic acid and its mixture, pimelic acid, suberic acid, nonyl two
Acid, heneicosanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), heptadecane diacid, octadecane two
One of acid.
4. a kind of high-performance heat resistant polyamide according to Claims 2 or 3, which is characterized in that component (B) described dicarboxylic acids
For one of adipic acid, decanedioic acid and M-phthalic acid.
5. a kind of high-performance heat resistant polyamide according to claim 1, which is characterized in that the component (C) antioxygen
Agent is one or more of phosphoric acid, phosphorous acid, hypophosphorous acid.
6. a kind of high-performance heat resistant polyamide described in -5 any claims according to claim 1, which is characterized in that the height
The melt temperature scope of performance heat resistant polyamide is 260-320 DEG C, and glass transition temperature is greater than 135 DEG C.
7. a kind of high-performance heat resistant polyamide described in -5 any claims according to claim 1, which is characterized in that the height
The heat resistant polyamide of performance heat resistant polyamide compared with the prior art, under identical fusing point, viscosity and molecular mass regimes, melting
Index improves 10-40g/10min, and processing temperature reduces at least 10 DEG C.
8. a kind of preparation method of high-performance heat resistant polyamide according to claim 1, which is characterized in that including following step
It is rapid:
S1, methyl cyclohexane diamines, terephthalic acid (TPA) and water being placed in the first salt dissolving tank, heating salt-forming reaction obtains component (A),
Methyl cyclohexane diamines or diamines, dicarboxylic acids and water are placed in the second salt dissolving tank, heating salt-forming reaction obtains component (B), at salt
After the completion, component (A), component (B) and component (C) are put into polymeric kettle；
S2, using air in carbon dioxide replacement kettle, at least twice；
S3, heating polymeric kettle open stirring until when temperature in the kettle reaches 150-170 DEG C, continue to be heated to temperature in the kettle to reach
220-280 DEG C, pressure 1.5-2.5MPa, heat-insulation pressure keeping are reacted；
When material solid content is 70% in S4, measurement kettle, slow pressure release, until stopping heating when material solid content is 80% in kettle
And stirring, prepolymer in kettle is sprayed, obtained solid product cools down under a nitrogen, obtains solid prepolymer；
S5, S4 obtained solid prepolymer is dried, puts into solid phase kettle, heats under nitrogen protection, be warming up to 220-260
DEG C, heat-insulation pressure keeping reacts 8-12h, and discharging obtains the high-performance heat resistant polyamide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112473610A (en) * | 2020-10-31 | 2021-03-12 | 山东广垠新材料有限公司 | Process and apparatus for melt polymerization of semi-aromatic polyamides |
| CN113136030A (en) * | 2021-05-14 | 2021-07-20 | 郑州大学 | Polyamide derived from monomer containing single six-membered alicyclic structure and preparation method thereof |
| CN114507343A (en) * | 2022-03-09 | 2022-05-17 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
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| CN105295030A (en) * | 2014-06-20 | 2016-02-03 | Ems专利股份公司 | Composite comprising a matrix material made of an amorphous polyamide and use thereof |
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| CN106916294A (en) * | 2015-12-25 | 2017-07-04 | 大连理工常熟研究院有限公司 | The preparation method and Semi-aromatic transparent polyamide of a kind of Semi-aromatic transparent polyamide |
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Patent Citations (4)
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| CN103665372A (en) * | 2012-09-06 | 2014-03-26 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof, and semi-aromatic polyamide composition and application thereof |
| CN105295030A (en) * | 2014-06-20 | 2016-02-03 | Ems专利股份公司 | Composite comprising a matrix material made of an amorphous polyamide and use thereof |
| CN105330847A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Synthetic method of high-fluidity transparent polyamide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112473610A (en) * | 2020-10-31 | 2021-03-12 | 山东广垠新材料有限公司 | Process and apparatus for melt polymerization of semi-aromatic polyamides |
| CN113136030A (en) * | 2021-05-14 | 2021-07-20 | 郑州大学 | Polyamide derived from monomer containing single six-membered alicyclic structure and preparation method thereof |
| CN114507343A (en) * | 2022-03-09 | 2022-05-17 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
| CN114507343B (en) * | 2022-03-09 | 2024-03-22 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
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