CN108192094A - The preparation method of PA (6-co-6T) copolymer - Google Patents
The preparation method of PA (6-co-6T) copolymer Download PDFInfo
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- CN108192094A CN108192094A CN201810115469.8A CN201810115469A CN108192094A CN 108192094 A CN108192094 A CN 108192094A CN 201810115469 A CN201810115469 A CN 201810115469A CN 108192094 A CN108192094 A CN 108192094A
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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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic 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
- C08G69/04—Preparatory processes
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Abstract
The present invention relates to a kind of preparation method of PA (6 co 6T) copolymer, including：Using hexamethylene diamine and acid donors as polymerized monomer, pass through melt polycondensation reaction, PA (6 co 6T) copolymer of molten state is made, the acid donors are made of terephthalic acid (TPA) and caprolactam, and molar percentage of the terephthalic acid (TPA) in acid donors is less than 60%.Present inventors have unexpectedly found that by adjusting the content of aromatic units, PA (6 co 6T) copolymer of molten state can be made, discharging is very convenient.
Description
Technical field
The present invention relates to IPC classification C08L77/06 " polyamide obtained by polyamine and polybasic carboxylic acid ".
Background technology
Nylon is invented by DuPont Corporation and first by its commercialization, also known as polyamide, in foundation backbone structure whether
Containing aromatic ring, two class of aliphatic and aromatic series can be divided into.The preparation method of nylon have low-temperature solution polycondensation, interface polycondensation,
Phosphonylation method, ionic liquid synthetic method, direct melt polycondensation method, the acylation condensation methods of palladium chtalyst, ester amine exchange process, gas phase are gathered
Legal, aqueous phase solution condensation methods and process for solid state polycondensation.
After invention amorphous nylon first, aromatic polyamide is also succeeded in developing first by DuPont Corporation, is had
Higher heat resistance.The aromatic nylon of external industrialized production has PA6T, PA9T, MXD6 etc., and the country is mainly golden hair
The PA10T of scientific and technological development, it is most to be that domestic enterprise applies for a patent.
It is difficult since its fusing point is higher than its heat decomposition temperature although document report PA6T costs are relatively low, water absorption rate is moderate
To carry out melt-processed molding, generally use copolymerization or the method modification being blended are melted with realizing, copolymer is generally termed as PA
(X-co-6T), X represents the nylon of copolymerization.Mitsui chemical company has developed modified Pa 6 T, and Authorization Notice No. is
The patent of JP2928325 discloses incorporation M-phthalic acid and PA6T modifiers is made.Fusion method is taken to prepare PA6T copolymerization at present
Object will generally mix M-phthalic acid, long-chain biatomic acid etc..
By taking PA (6-co-6T) as an example, interface polycondensation is comparatively laborious, does not mix M-phthalic acid when other monomers, by
In being difficult to direct melt polycondensation, during prior art preparation PA (6-co-6T) copolymer, be substantially 200-220 DEG C or so into
Row precondensation obtains solid product, then through Low Temperature Solid-Phase polycondensation or in screw extruder melt polycondensation to improve the degree of polymerization,
But it is inconvenient that precondensation product takes out, and is unfavorable for following process.
Invention content
Present inventors have unexpectedly found that other monomers are not mixed, it is also fusible to prepare PA (6-co-6T) copolymer, preparation method
Condition it is also not harsh.
On the one hand, the present invention provides the preparation method of PA (6-co-6T) copolymer, including：
Using hexamethylene diamine and acid donors as polymerized monomer, by melt polycondensation reaction, the PA (6-co-6T) of molten state is made altogether
Polymers, the acid donors are made of terephthalic acid (TPA) and caprolactam, and molar percentage of the terephthalic acid (TPA) in acid donors is (again
Claim aromatic units or 6T unit contents) less than 60%, preferably no more than 40%, more preferably 20-40%；Certainly, this field
It is well known that the form that starting material provides polymerized monomer is unrestricted, it is free that the hexamethylene diamine, terephthalic acid (TPA) can cover it
The form of the soda acid of state and equivalent nylon salt, the oligomer containing the polymerized monomer or even entirely with poly- in starting material
The oligomer form for closing monomer provides, and for further polycondensation, the variation of these forms does not interfere with terephthalic acid (TPA) in acid donors
In molar percentage.
Optionally, the reaction temperature of the melt polycondensation reaction be 320 DEG C hereinafter, preferably 310 DEG C hereinafter, such as 280-
310 DEG C, be for another example 280-290 DEG C or 290-310 DEG C.
Optionally, hexamethylene diamine compares acid donors excess 1-5%, preferably 3-4% in the polymerized monomer.Oneself in raw material
Diamines is usually provided with free alkali form, the inventors discovered that, hexamethylene diamine is excessive, conducive to the raising of the product degree of polymerization.
Optionally, the preparation method further includes：By PA (6-co-6T) copolymer of molten state, by solid phase polycondensation or
Melt polycondensation is to further improve the performances such as the degree of polymerization in screw extruder.
Optionally, the preparation method includes the removing of the hexamethylene diamine of the water and/or excess in removing polycondensation reaction system
Operation is especially included in during melt polycondensation reaction carries out or after carrying out, and carries out the removing operation；Removing operation is usually to put
Gas.The inventors discovered that being operated by the removing, not only carried out, but also reduce the pressure of reaction system, carried conducive to polycondensation reaction
High product quality.
Optionally, before melt polycondensation reaction is carried out, progress prepolymerization reaction obtains PA (6-co- at 200-220 DEG C
6T) oligomer；Optionally, before melt polycondensation reaction required temperature is risen to, the PA (6-co-6T) oligomer is further contracted
Poly-, this operation may include 1-3 heating, such as first rises to 250 DEG C, then rise to 260 DEG C, finally rises to 280-320 DEG C and melted again
Melt polycondensation reaction.
Optionally, before polycondensation reaction is carried out, 200-220 DEG C is directly warming up to, acid donors are made during heating to benzene
Dioctyl phthalate forms nylon salt in water with hexamethylene diamine, and caprolactam is also hydrolyzed into nylon salt, and salt time, the dosage of water regard need to
Depending on wanting, e.g., heat up total time, can be 1-3h；The dosage that water is corresponded to per mol hexamethylene diamines is usually 100-300mL, such as 110-
240mL.The inventors discovered that without monomer is made nylon salt form in advance, even without individual insulation reaction into salt, directly
It is connected in temperature-rise period into salt, this is also conducive to be carried out continuously subsequent polycondensation reaction.
Optionally, during the preparation method is raw materials used, the molar ratio of caprolactam and terephthalic acid (TPA) is 1.5-4：1,
The preparation method includes the following steps：
1) reaction system is warming up to 200-220 DEG C in 1-3h (such as 2h), is then depressurized to 0.1-2MPa,
2) reaction system is warming up to 280-310 DEG C needed for melt polycondensation reaction, the melt polycondensation reaction time can be
Then 30min is depressurized to normal pressure, obtain PA (6-co-6T) copolymer of molten state.
Optionally, during the preparation method is raw materials used, the molar ratio of caprolactam and terephthalic acid (TPA) is 1.5-4：1,
The preparation method includes the following steps：
1) reaction system is warming up to 220 DEG C in 1-3h (such as 2h), is then depressurized to 0.1-2MPa,
2) reaction system is warming up to 250 DEG C in 1-3h (such as 2h), is then depressurized to 0.1-3MPa,
3) reaction system is warming up to 260 DEG C, is then depressurized to 0.1-1MPa,
4) reaction system is warming up to 280-310 DEG C needed for melt polycondensation reaction, carries out melt polycondensation reaction, melted
Melt PA (6-co-6T) copolymer of state.
Optionally, the preparation method also uses catalyst and makees raw material, and the catalyst is selected from sodium phosphite, secondary phosphorous
Any one or a few in sour sodium, ortho phosphorous acid potassium, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc, catalyst are used
Amount can be the 0.1-0.3% of polymerized monomer raw material gross weight, such as be 0.2-0.3%.
Aforementioned reduced pressure operation can be can be realized by simply deflating；Reaction can carry out under stiring, and mixing speed can
For 100-150r/min.After melt polycondensation reaction, normal pressure is down to, directly can discharge or discharge and is more convenient, it is lazy by being filled with
Property gas pressurized.
On the other hand, the present invention provides the PA of molten state (6-co-6T) copolymer, in PA (6-co-6T) copolymer
The molar percentage of 6T units is less than 60%, is such as preferably no more than 40%, more preferably 20-40% less than 50%；Copolymerization
The intrinsic viscosity of object can be 0.967-1.029dL/g.Catalyst containing a small amount of (such as 0.1-0.3wt%) in the copolymer,
The catalyst is selected from sodium phosphite, sodium hypophosphite, ortho phosphorous acid potassium, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid
Any one or a few in zinc.The copolymer can be prepared by method noted earlier.
The core of the present invention has the beneficial effect that：
Inventors have surprisingly discovered that by adjusting the content of aromatic units, PA (6-co-6T) copolymerization of molten state can be made
Object, discharging is very convenient, even without inert gas is filled with to discharge, conducive to subsequent processing.The present invention can be in rather low temperature
Degree is lower to carry out melt polycondensation, and reaction is more easy to control.The pressure of polycondensation reaction system of the present invention is than relatively low, the requirement to equipment
It is few.The copolymer fusing point of gained of the invention is low, the degree of polymerization, good mechanical property.
Specific embodiment
Primary raw material and abbreviation：Caprolactam (CPL)；Terephthalic acid (TPA) (PTA)；Hexamethylene diamine (HMDA)；Sodium hypophosphite
(NaH2PO2·H2O)
Fusing point is tested using DSC in following embodiments, using the temperature of melting peak as fusing point；Intrinsic viscosity is with dense
Sulfuric acid is solvent, is obtained with Ubbelohde viscometer survey calculation.
Embodiment 1：
By PTA33.20g (0.2mol), CPL90.54g (0.8mol), HMDA24.18g (0.208mol), sodium hypophosphite
0.444g and water 240mL are added in the autoclave of 1L, after being passed through nitrogen pressure testing 3 times, open stirring (100r/min), and start to rise
Temperature slowly increases system temperature to 220 DEG C in 2h, opens deflation valve and deflates, pressure in kettle is made to be reduced to 2MPa.Then exist
250 DEG C are warming up in 2h, deflation valve is opened and deflates, pressure in kettle is made to be reduced to 3MPa.Continuing heating increases temperature in the kettle
To 260 DEG C, open deflation valve and deflate, pressure in kettle is made to be reduced to normal pressure.Continue heating and treat that temperature in the kettle is increased to 280 DEG C,
It opens vent valve and is deflated to normal pressure, nitrogen is then led into kettle, then open bottom baiting valve, molten state product is picked up with porcelain tray
(product is white, intrinsic viscosity 0.967dL/g), obtains PA (6-co-6T) copolymer that aromatic units content is 20%, melts
Point is 242 DEG C.
Embodiment 2：
By PTA66.40g (0.4mol), CPL67.90g (0.6mol), HMDA47.90g (0.412mol), sodium hypophosphite
0.38g and water 240mL are added in the autoclave of 1L, after being passed through nitrogen pressure testing 3 times, open stirring (100r/min), and start to rise
Temperature slowly increases system temperature to 220 DEG C in 2h, opens deflation valve and deflates, pressure in kettle is made to be reduced to 2MPa.Then exist
250 DEG C are warming up in 2h, deflation valve is opened and deflates, pressure in kettle is made to be reduced to 3MPa.Continuing heating increases temperature in the kettle
To 260 DEG C, open deflation valve and deflate, pressure in kettle is made to be reduced to normal pressure.Continue heating and treat that temperature in the kettle is increased to 290 DEG C,
It opens vent valve and is deflated to normal pressure, nitrogen is then led into kettle, then open bottom baiting valve, molten state product is picked up with porcelain tray
(product is white, intrinsic viscosity 1.029dL/g), obtains PA (6-co-6T) copolymer that aromatic units content is 40%, melts
Point is 260 DEG C.
Contrast experiment：
The molar ratio for adjusting PTA and ADA in reaction raw materials is 3:2 (i.e. 6T unit contents are 60%), other are completely by real
The condition for applying example 1 or 2 is reacted, as a result, it has been found that, product can not melt；The temperature of melt polycondensation reaction is only changed to higher
290-310 DEG C, repeat Examples 1 and 2, it is found that product is still fusible, and PTA：ADA=3:2 comparative example, still can not be real
Existing product melt.
Claims (10)
- The preparation method of 1.PA (6-co-6T) copolymer, including：Using hexamethylene diamine and acid donors as polymerized monomer, by melt polycondensation reaction, PA (6-co-6T) copolymerization of molten state is made Object, the acid donors are made of terephthalic acid (TPA) and caprolactam, and molar percentage of the terephthalic acid (TPA) in acid donors is less than 60%；Optionally, reaction has used catalyst, and the catalyst is selected from sodium phosphite, sodium hypophosphite, ortho phosphorous acid potassium, secondary Any one or a few in phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc.
- 2. preparation method as described in claim 1, it is characterized in that, the reaction temperature of the melt polycondensation reaction for 320 DEG C with Under, preferably 310 DEG C hereinafter, such as 280-310 DEG C, be for another example 280-290 DEG C or 290-310 DEG C.
- 3. preparation method as described in claim 1, it is characterized in that, molar percentage of the terephthalic acid (TPA) in acid donors Such as it is 20-40% less than 40%.
- 4. preparation method as described in claim 1, it is characterized in that, hexamethylene diamine compares terephthalic acid (TPA) mistake in the polymerized monomer Measure 1-5%, preferably 3-4%.
- 5. preparation method as described in claim 1, it is characterized in that, the preparation method further includes following steps：Before melt polycondensation reaction is carried out, progress prepolymerization reaction obtains PA (6-co-6T) oligomer at 200-220 DEG C.
- 6. preparation method as claimed in claim 5, it is characterized in that, the preparation method further includes following steps：It is before melt polycondensation reaction required temperature is risen to, PA (6-co-6T) oligomer obtained by the prepolymerization reaction is further Polycondensation.
- 7. the preparation method as described in any first claim, it is characterized in that, the preparation method include containing acid donors and The aqueous solution of hexamethylene diamine, which directly heats up, is made nylon salt, then carries out polycondensation reaction.
- 8. the preparation method as described in any first claim, it is characterized in that, the preparation method includes the following steps：1) reaction system in 1-3h is warming up to 200-220 DEG C, then is depressurized to 0.1-2MPa,2) reaction system is warming up to 280-310 DEG C needed for melt polycondensation reaction, carries out melt polycondensation reaction, obtain molten state PA (6-co-6T) copolymer.
- 9. preparation method as claimed in claim 8, it is characterized in that, further include following steps between the step 1 and 2：A) reaction system in 1-3h is warming up to 250 DEG C, be then depressurized to 0.1-3MPa,Optionally continue step b,B) reaction system is warming up to 260 DEG C, is then depressurized to 0.1-1MPa.
- 10. the preparation method as described in any first claim, it is characterized in that, it is anti-that the preparation method further includes removing polycondensation Answer the hexamethylene diamine of the water and/or excess in system.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081222A (en) * | 1987-07-17 | 1992-01-14 | Basf Aktiengesellschaft | Partly aromatic copolyamide of reduced triamine content |
| CA2066106A1 (en) * | 1991-04-16 | 1992-10-17 | Walter Goetz | Stabilized thermoplastic partly aromatic polyamide molding compositions |
| KR0178054B1 (en) * | 1993-06-05 | 1999-05-15 | 구창남 | Process for preparing polyamide having excellent thermal shrinkage stability |
| CN105085903A (en) * | 2015-09-14 | 2015-11-25 | 北京旭阳化工技术研究院有限公司 | High-temperature-resistant branched polyamide block copolymer and preparation method thereof |
| CN105175715A (en) * | 2014-05-30 | 2015-12-23 | 财团法人工业技术研究院 | Copolymer, and method for preparing a monomer used to form the copolymer |
-
2018
- 2018-02-06 CN CN201810115469.8A patent/CN108192094B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081222A (en) * | 1987-07-17 | 1992-01-14 | Basf Aktiengesellschaft | Partly aromatic copolyamide of reduced triamine content |
| CA2066106A1 (en) * | 1991-04-16 | 1992-10-17 | Walter Goetz | Stabilized thermoplastic partly aromatic polyamide molding compositions |
| KR0178054B1 (en) * | 1993-06-05 | 1999-05-15 | 구창남 | Process for preparing polyamide having excellent thermal shrinkage stability |
| CN105175715A (en) * | 2014-05-30 | 2015-12-23 | 财团法人工业技术研究院 | Copolymer, and method for preparing a monomer used to form the copolymer |
| CN105085903A (en) * | 2015-09-14 | 2015-11-25 | 北京旭阳化工技术研究院有限公司 | High-temperature-resistant branched polyamide block copolymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 周祥兴: "《中国塑料制品配方大全 》", 31 May 1995, 中国物资出版社 * |
| 张春祥 等: "半芳香共聚尼龙6T／6 的合成与表征", 《工程塑料应用》 * |
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