CN102453255B - Semi-aromatic polyamide polyester copolymer and preparation method thereof - Google Patents
Semi-aromatic polyamide polyester copolymer and preparation method thereof Download PDFInfo
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- CN102453255B CN102453255B CN 201010520282 CN201010520282A CN102453255B CN 102453255 B CN102453255 B CN 102453255B CN 201010520282 CN201010520282 CN 201010520282 CN 201010520282 A CN201010520282 A CN 201010520282A CN 102453255 B CN102453255 B CN 102453255B
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Abstract
The invention provides a semi-aromatic polyamide polyester copolymer, which is characterized in that: the structural formula of the semi-aromatic polyamide polyester copolymer is (AB)n, wherein m1 is an integer from 1 to 500; m2 is an integer from 1 to 500; and n is an integer from 10 to 500. The invention also provides a method for preparing the semi-aromatic polyamide polyester copolymer. The semi-aromatic polyamide polyester copolymer has high heat resistance, water absorbability and mechanical properties; and the preparation method is simple, molecular structures are controllable, a few side reactions are carried out, and the conversion rate of the product is high.
Description
Technical field
The invention belongs to polymeric material field, relate in particular to a kind of Semi-aromatic polyamide polyester copolymer and preparation method thereof.
Background technology
Semi-aromatic polyamide has excellent high thermal resistance, self lubricity, intensity, toughness, but has simultaneously the shortcomings such as cost is high, shrinking percentage is large, water-absorbent is strong, dimensional stability is bad; And the water-intake rate of polyester (PCT) is lower, and shrinking percentage is little, but its high thermal resistance, self lubricity, intensity, toughness are relatively poor again.
Disclose a kind of preparation method of thermosetting polyamide ester in the prior art, obtained two acid diesters by adopting the reaction of aromatic dibasic acid acid anhydride and monohydroxy-alcohol, carry out chloride by thionyl chloride in the high-melting-point solvent, cooling obtains the solid solution of diester diacid chloride; Then the solution with the aprotic polar solvent of diamines carries out liquid-solid two alternate polycondensations, thereby makes polyesteramide.The polyesteramide that this preparation method obtains is thermosetting material, can not carry out subsequent forming processing, so Application Areas is received greatly restriction.
In the prior art semi-aromatic polyamide and polyester are carried out copolymerization, but be difficult to control ester group, the amide group content of molecular structure in the copolymerization produce, cause thermotolerance, water-absorbent and the mechanicalness of multipolymer relatively poor; Other low conversion rate.
Summary of the invention
Thermotolerance, water-absorbent and the mechanical property that the invention solves the polyesteramide that exists in the prior art is relatively poor, the technical problem of low conversion rate.
The invention provides a kind of Semi-aromatic polyamide polyester copolymer, the structural formula of described semi-aromatic polyamide polyester is (AB)
n
A is:
B is:
Wherein, m
1Integer for 1-500; m
2Integer for 1-500; N is the integer of 10-500.
The present invention also provides the preparation method of described Semi-aromatic polyamide polyester copolymer, may further comprise the steps:
1) 1,4 cyclohexane dimethanol and hexanediamine equimolar ratio is soluble in water, obtain mixing solutions; In mixing solutions, add acid absorber, and guarantee that the temperature of mixing solutions is 5-25 ℃;
2) p-phthaloyl chloride is dissolved in the methylene dichloride, obtains paraphenylene terephthalamide's chlorine solution; Under the whipped state, paraphenylene terephthalamide's chlorine solution is dropwise added in the mixing solutions of step 1); Dripping rear continuation stirs;
3) filtration step 2) product, the washing, ammonia scrubbing, drying obtains described Semi-aromatic polyamide polyester copolymer.
The present invention is by adopting p-phthaloyl chloride and 1,4 cyclohexanedimethanols, hexanediamine polymerization reaction take place, contain high-temperature polyester unit and semi-aromatic polyamide unit in the main polymer chain introducing, thus but thermotolerance, water-absorbent and the mechanical property of Effective Raise polymeric amide polyester copolymer of the present invention.And preparation method's technique provided by the invention is simple, and molecular structure is controlled, side reaction is few, and conversion rate of products is high.
Embodiment
The invention provides a kind of Semi-aromatic polyamide polyester copolymer, the structural formula of described semi-aromatic polyamide polyester is (AB)
n
A is:
B is:
Wherein, m
1Integer for 1-500; m
2Integer for 1-500; N is the integer of 10-500.
In the Semi-aromatic polyamide polyester copolymer provided by the invention, (1) is contained amide group (NH-CO-), each amide group one end is linked to each other with phenyl ring, and the other end connects fatty carbon chain, namely forms semi-aromatic polyamide; (2) contain ester group (COO-), an end of ester group links to each other with phenyl ring, the other end with
Connect; Therefore, Semi-aromatic polyamide polyester copolymer of the present invention had both had high thermal resistance, oilness, intensity, the toughness of semi-aromatic polyamide, had again the lower water-intake rate of polyester and shrinking percentage; (3) contain
Repeating unit is so that Semi-aromatic polyamide polyester copolymer of the present invention has high-temperature polyester PCT(poly terephthalic acid 1,4 cyclohexane dimethanol ester) resistance to elevated temperatures.The viscosity-average molecular weight of described Semi-aromatic polyamide polyester copolymer is 1.0-2.1dl/g, is preferably 1.2-1.8 dl/g.
Under the preferable case, m1 is the integer of 1-100; m
2Integer for 1-100; N is the integer of 20-500.
Among the present invention, the molar percentage of A and B is 10-90:90-10, i.e. m
1: m
2=10-90:90-10.
The present invention also provides the preparation method of described Semi-aromatic polyamide polyester copolymer,, may further comprise the steps:
1) 1,4 cyclohexane dimethanol and hexanediamine equimolar ratio is soluble in water, obtain mixing solutions; In mixing solutions, add acid absorber, and guarantee that the temperature of mixing solutions is 5-25 ℃;
2) p-phthaloyl chloride is dissolved in the methylene dichloride, obtains paraphenylene terephthalamide's chlorine solution; Under the whipped state, paraphenylene terephthalamide's chlorine solution is dropwise added in the mixing solutions of step 1); Dripping rear continuation stirs;
3) filtration step 2) product, the washing, ammonia scrubbing, drying obtains described Semi-aromatic polyamide polyester copolymer.
Preparation method provided by the invention, adopt 1,4 cyclohexanedimethanols, hexanediamine and p-phthaloyl chloride are as monomer, by 1, the amidation polycondensation of esterifying polycondensation reaction, hexanediamine and the p-phthaloyl chloride of 4 cyclohexanedimethanols and p-phthaloyl chloride, thus Semi-aromatic polyamide polyester copolymer of the present invention can be obtained.Concrete reaction mechanism is as follows:
In the reaction process, the too low then speed of response of system temperature is too slow, and acyl chlorides reacts for a long time and can produce hydrolysis, reduces transformation efficiency; The too high then acyl chloride reaction of system temperature is too fierce, is difficult to control.Therefore, among the present invention, need the control temperature of reaction within the specific limits.During particularly, preparation steps 1) mixing solutions, guarantee that the temperature of mixing solutions is 5-25 ℃.
Among the present invention, fully react for making Isosorbide-5-Nitrae cyclohexanedimethanol, hexanediamine and p-phthaloyl chloride, need first Isosorbide-5-Nitrae cyclohexanedimethanol, hexanediamine equimolar ratio soluble in waterly, be mixed with mixing solutions.During the preparation mixing solutions, the consumption of water is too much unsuitable, in order to avoid reactant concn is too low, the reaction times lengthens.Under the preferable case, in the described mixing solutions of step 1), take the water of 100 weight parts as benchmark, the total mass of Isosorbide-5-Nitrae cyclohexanedimethanol, hexanediamine, acid absorber is the 3-9 weight part.
According to the described reaction mechanism of following formula, in the polycondensation process, can produce a large amount of hydrogenchloride, the acidity of augmenting response system hinders proceeding of reaction.Therefore, among the present invention, also need add the hydrogenchloride of in time consumption reaction generation of acid absorber, improve the transformation efficiency of Semi-aromatic polyamide polyester copolymer of the present invention.Described acid absorber is various alkali commonly used in the prior art, for example can be sodium hydroxide or potassium hydroxide.According to reaction mechanism, nm
1The Isosorbide-5-Nitrae cyclohexanedimethanol of mol, n (m
1+ m
2) p-phthaloyl chloride and the nm of mol
2The hexanediamine of mol, the hydrogenchloride that reaction produces is 2n (m
1+ m
2) mol.Therefore, be fully absorbed neutralization for guaranteeing hydrogenchloride, the mol ratio of p-phthaloyl chloride and acid absorber is 1:2.
In like manner, fully react for making Isosorbide-5-Nitrae cyclohexanedimethanol, hexanediamine and p-phthaloyl chloride, also need among the present invention p-phthaloyl chloride is dissolved in the methylene dichloride, be mixed with paraphenylene terephthalamide's chlorine solution.In the preparation paraphenylene terephthalamide chlorine solution process, the consumption of methylene dichloride is too much unsuitable, in order to avoid paraphenylene terephthalamide's cl concn is too low, the reaction times lengthens.Under the preferable case, the mass ratio of p-phthaloyl chloride and methylene dichloride is 1:2.5-10.
As a kind of preferred implementation of the present invention, for effectively controlling the extent of polymerization of Isosorbide-5-Nitrae cyclohexanedimethanol, hexanediamine, p-phthaloyl chloride among the present invention, also can in reaction system, add an amount of Benzoyl chloride.Described Benzoyl chloride can add in the mixing solutions simultaneously with p-phthaloyl chloride.Under the preferable case, can first Benzoyl chloride be added in paraphenylene terephthalamide's chlorine solution.Take the total amount of p-phthaloyl chloride as benchmark, the consumption of Benzoyl chloride is 0.01-5mol%.
According to reaction mechanism, nm
1The Isosorbide-5-Nitrae cyclohexanedimethanol of mol, nm
2The hexanediamine of mol and n (m
1+ m
2) p-phthaloyl chloride of mol fully reacts, and obtains Semi-aromatic polyamide polyester copolymer of the present invention.Therefore, the mole number of p-phthaloyl chloride equals the mole number sum of Isosorbide-5-Nitrae cyclohexanedimethanol and hexanediamine.
Under the preferable case, possesses simultaneously the performance of semi-aromatic polyamide and high-temperature polyester, the mol ratio 10-90:90-10 of Isosorbide-5-Nitrae cyclohexanedimethanol and hexanediamine for guaranteeing Semi-aromatic polyamide polyester copolymer of the present invention.
According to preparation method provided by the invention, under whipped state, the adding of paraphenylene terephthalamide's chlorine solution is contained in the mixing solutions of Isosorbide-5-Nitrae cyclohexanedimethanol and hexanediamine.The mode that dropwise adds is adopted in the adding of paraphenylene terephthalamide's chlorine solution, and the speed of dropping can not be too fast, fully reacts to guarantee p-phthaloyl chloride and Isosorbide-5-Nitrae cyclohexanedimethanol, hexanediamine.Under the preferable case, the time for adding of paraphenylene terephthalamide's chlorine solution is 1-10min.After paraphenylene terephthalamide's chlorine solution is added dropwise to complete, also need continue to stir; The time of continuing to stir is 5-30min.
After reaction is finished, obtain containing the mixed system of gluey Semi-aromatic polyamide polyester copolymer of the present invention.Filter this mixed system, filter residue is gluey Semi-aromatic polyamide polyester copolymer.Successively to filter residue wash, ammonia scrubbing.Wherein, deionized water is adopted in washing, and the number of times of washing is not particularly limited, and for example can wash 3 times.
After washing is finished, the washing product is carried out ammonia scrubbing.Ammonia scrubbing is used for removing the HCl that residues in product.During ammonia scrubbing, adopt the concentration of ammoniacal liquor unsuitable too high, with the Semi-aromatic polyamide polyester copolymer hydrolysis that prevents from generating.Under the preferable case, ammonia scrubbing can adopt the ammonia soln of 2-12wt%.The number of times of ammonia scrubbing is not particularly limited, and is 7 ± 0.1 to get final product to the pH value of wash filtrate.
After ammonia scrubbing is finished, with filter residue and drying, can obtain Semi-aromatic polyamide polyester copolymer of the present invention.Wherein, drying can adopt and well known to a person skilled in the art various drying meanss, and the present invention does not have particular determination.For example, the filter residue behind the ammonia scrubbing can be placed vacuum drying oven, be that ﹣ 0.09Mpa, temperature are to dry under 120 ℃ the condition in vacuum tightness.
The invention will be further described below in conjunction with embodiment.The raw material that adopts in embodiment and the Comparative Examples all is commercially available.
Embodiment 1
In the 1L four neck flasks that agitator, dropping funnel, thermometer and charging opening are housed, with 7.21g(0.05mol) 1.4-cyclohexanedimethanol and 5.81g(0.05mol) hexanediamine and 8g(0.2mol) dissolution of sodium hydroxide is in 500ml water, and the temperature that keeps flask interior solution is at 15 ℃.
In beaker with 20.3g(0.1mol) p-phthaloyl chloride and 0.14g (0.001mol) Benzoyl chloride be dissolved in the 130ml methylene dichloride, resulting solution added in the dropping funnel of four neck flasks; Under the whipped state, the solution in the dropping funnel dropwise adds in the four neck flasks, dropwises in the 2min; Drip off rear continuation high-speed stirring 10min.
Product in the four neck flasks is filtered, and filter residue under agitation washs 3min with the 500ml deionized water; Repeated washing 3 times.Then be that the ammonia soln 500ml of 7.5 % by weight under agitation washs 3h with concentration; Repeated washing to the pH value of wash filtrate is 7 ± 0.1.
Filtration product after the washing is placed in the vacuum drying oven (upper the grand experimental installation of Nereid company limited, model is the DZF-6020 type), and vacuum tightness is-0.09MPa, and temperature is dry 4h under 120 ℃ the condition; Cooling obtains the product Semi-aromatic polyamide polyester copolymer, is designated as S1; The 24.6g that weighs, transformation efficiency is 95%.
Embodiment 2
Adopt the step identical with embodiment 1 to prepare the Semi-aromatic polyamide polyester copolymer S2 of the present embodiment, difference is: the consumption of Isosorbide-5-Nitrae cyclohexanedimethanol is 1.442g(0.01mol), the consumption of hexanediamine is 10.458g(0.09mol).
By above-mentioned steps, obtain product Semi-aromatic polyamide polyester copolymer S2; The 23.9g that weighs, transformation efficiency is 96%.
Embodiment 3
Adopt the step identical with embodiment 1 to prepare the Semi-aromatic polyamide polyester copolymer S3 of the present embodiment, difference is: the consumption of Isosorbide-5-Nitrae cyclohexanedimethanol is 12.978g(0.09mol), the consumption of hexanediamine is 1.162(0.01mol).
By above-mentioned steps, obtain product Semi-aromatic polyamide polyester copolymer S3; The 25.8g that weighs, transformation efficiency is 95%.
Embodiment 4
Adopt the step identical with embodiment 1 to prepare the Semi-aromatic polyamide polyester copolymer S3 of the present embodiment, difference is: the consumption of water is 450mL; The consumption of methylene dichloride is 150mL; Ammonia scrubbing adopts the ammonia soln of 10wt%.
By above-mentioned steps, obtain product Semi-aromatic polyamide polyester copolymer S4; The 24.3g that weighs, transformation efficiency is 94%.
Performance test:
1, viscosity-average molecular weight: adopt Ubbelodhe viscometer to carry out;
2, limiting viscosity (η): carry out according to ISO 307 disclosed methods;
3, melt temperature (Tm) and second-order transition temperature (Tg): adopt thermogravimetric analyzer (TA, DSC-Tg), in nitrogen atmosphere, be warming up to 500 ℃ with the temperature rise rate of 10 ℃/min and carry out;
4, saturated water absorption (in 23 ℃ of water) and rate of moisture absorption (23 ℃/50% relative humidity): carry out according to ISO 62 disclosed methods;
5, tensile modulus: carry out according to the disclosed method of ISO 527-2;
6, modulus in flexure: carry out according to ISO 178 disclosed methods;
7, notched Izod impact strength (+23 ℃): carry out according to the disclosed method of ISO 179/1eU.
According to above-mentioned testing method to the resulting product S 1-S4 of embodiment 1-4 and semi-aromatic polyamide (PA6T/66) (BASF, the trade mark: C215), poly terephthalic acid-1,4-cyclohexanedimethanoester ester (PCT) (Dupont, Thermx TE4007 WT538) test, test result is as shown in table 1.
Table 1
| Test | S1 | S2 | S3 | S4 | PA6T/66 | PCT |
| η（dl/g） | 1.28 | 1.36 | 1.42 | 1.32 | 1.3 | 1.5 |
| Tm（℃） | 310 | 315 | 307 | 309 | 320 | 290 |
| Tg（℃） | 130 | 138 | 129 | 131 | 140 | 125 |
| Saturated water absorption (%) | 2.9 | 3.3 | 1.6 | 2.8 | 7.3 | 0.5 |
| Saturated rate of moisture absorption (%) | 0.8 | 1.2 | 0.6 | 1.3 | 2 | 0.25 |
| Tensile modulus (MPa) | 3000 | 3100 | 2800 | 3000 | 3200 | 2600 |
| Modulus in flexure (MPa) | 2700 | 2800 | 2500 | 2700 | 2900 | 2300 |
| Notched Izod impact strength (KJ/m 2) | 10 | 11 | 8 | 10 | 13 | 6 |
Test result by upper table 1 can find out, the viscosity-average molecular weight of Semi-aromatic polyamide polyester copolymer S1-S4 of the present invention is 1.2-1.5 dl/g; The Tm of S1-S4 is 300-320 ℃, and Tg is 125-140 ℃, illustrates that Semi-aromatic polyamide polyester copolymer of the present invention has preferably thermotolerance, obviously is better than PCT; The saturated water absorption of S1-S4 is 1.5-3.0%, and saturated rate of moisture absorption is 0.5-1.5%, illustrates that Semi-aromatic polyamide polyester copolymer of the present invention has preferably water tolerance, than semi-aromatic polyamide PA6T/66 water-tolerant; The tensile modulus of S1-S4 is 2800-3100MPa, and modulus in flexure is 2500-2800MPa, and notched Izod impact strength is 8-11KJ/m
2, illustrate that Semi-aromatic polyamide polyester copolymer of the present invention has preferably mechanical property.Preparation method provided by the invention, technique is simple, more than the transformation efficiency of S1-S4 reaches up to 94%.
Claims (11)
1. the preparation method of a Semi-aromatic polyamide polyester copolymer may further comprise the steps:
1) 1,4 cyclohexane dimethanol and hexanediamine is soluble in water in proportion, obtain mixing solutions; In mixing solutions, add acid absorber, and guarantee that the temperature of mixing solutions is 5-25 ℃;
2) p-phthaloyl chloride is dissolved in the methylene dichloride, obtains paraphenylene terephthalamide's chlorine solution; Under the whipped state, paraphenylene terephthalamide's chlorine solution is dropwise added in the mixing solutions of step 1); Dripping rear continuation stirs;
3) filtration step 2) product, the washing, ammonia scrubbing, drying obtains described Semi-aromatic polyamide polyester copolymer;
The mol ratio of p-phthaloyl chloride and acid absorber is 1:2;
The structural formula of described semi-aromatic polyamide polyester is (AB)
n
A is:
B is:
Wherein, m
1Integer for 1-500; m
2Integer for 1-500; N is the integer of 10-500.
2. method according to claim 1 is characterized in that, m
1Integer for 1-100; m
2Integer for 1-100; N is the integer of 20-500.
3. method according to claim 2 is characterized in that, m
1: m
2=10-90:90-10.
4. method according to claim 1 is characterized in that, in the described mixing solutions of step 1), take the water of 100 weight parts as benchmark, the total mass of Isosorbide-5-Nitrae cyclohexanedimethanol, hexanediamine, acid absorber is the 3-9 weight part.
5. method according to claim 1 is characterized in that, acid absorber is sodium hydroxide or potassium hydroxide.
6. method according to claim 1 is characterized in that, p-phthaloyl chloride and methylene dichloride mass ratio are 1:2.5-10.
7. according to claim 1 or 6 described methods, it is characterized in that, also comprise the process that adds Benzoyl chloride in paraphenylene terephthalamide's chlorine solution; Take the amount of substance of p-phthaloyl chloride as benchmark, the consumption of Benzoyl chloride is 0.01-5mol%.
8. method according to claim 1 is characterized in that, the mole number of p-phthaloyl chloride is the mole number sum of Isosorbide-5-Nitrae cyclohexanedimethanol and hexanediamine.
9. according to claim 1 or 8 described methods, it is characterized in that the mol ratio 10-90:90-10 of Isosorbide-5-Nitrae cyclohexanedimethanol and hexanediamine.
10. method according to claim 1 is characterized in that, the time for adding of paraphenylene terephthalamide's chlorine solution is 1-10min; The time that drips rear continuation stirring is 5-30min.
11. method according to claim 1 is characterized in that, the ammonia soln of the 2-12wt% that ammonia scrubbing adopts.
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340885A (en) * | 1987-11-04 | 1994-08-23 | General Electric Company | Amide-ester copolymers and process for the preparation thereof |
| CN1214712A (en) * | 1996-02-05 | 1999-04-21 | 伊斯曼化学公司 | Polyester/polyesteramide blends |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340885A (en) * | 1987-11-04 | 1994-08-23 | General Electric Company | Amide-ester copolymers and process for the preparation thereof |
| CN1214712A (en) * | 1996-02-05 | 1999-04-21 | 伊斯曼化学公司 | Polyester/polyesteramide blends |
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