CN102344564B - Chain extender for polyamide preparation through chain extending - Google Patents
Chain extender for polyamide preparation through chain extending Download PDFInfo
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- CN102344564B CN102344564B CN201110198573A CN201110198573A CN102344564B CN 102344564 B CN102344564 B CN 102344564B CN 201110198573 A CN201110198573 A CN 201110198573A CN 201110198573 A CN201110198573 A CN 201110198573A CN 102344564 B CN102344564 B CN 102344564B
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- chainextender
- temperature
- multipolymer
- vinylbenzene
- polymethylmethacrylate
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Abstract
The invention relates to a chain extender for polyamide preparation through chain extending. The chain extender is prepared by the step of: reacting polymethyl methacrylate with styrene in a stainless steel reaction vessel equipped with a mixer, a condenser and a temperature control device as well as nitrogen atmosphere for 2-3h at a temperature of 108DEG C-112DEG C, thus obtaining a copolymer with a number-average molecular weight of 6000-7500 and a glass transition temperature of 50DEG C-60DEG C, with the styrene of 0.05 wt%-2 wt% in content. The invention also relates to application of the chain extender in a direct polymerization technology of polycaprolactam. Polycaprolactam slices obtained by a direct polymerization technology employing the chain extender have stable amino end group content, and high dyeing uniformity in a post processing process as well as good spinnability, thus being suitable for polyamide high-speed spinning and fine denier yarn production.
Description
Technical field
the present invention relates to a kind of chainextender, and particularly chemical chain extension legal system is equipped with the chainextender of polymeric amide.
Background technology
nylon (PA) not only has excellent mechanical property and electrical property preferably, but also has wear-resisting, oil resistant, anti-solvent, self-lubricating, self-extinguishing, erosion resistance and good processibility.
high viscosity nylon material is because its excellent mechanical property receives increasing concern in industrial application.In order to prepare full-bodied PA, can improve the vacuum ability through prolonging polymerization time; Method such as solid state polymerization and chemical chain extension obtains; But have certain difficulty, during like the prolongation polycondensation reaction time energy consumption is increased, production efficiency descends; And also cause the side reactions such as decomposition of product easily, and cause the finished product degradation; The solid state polymerization facility investment is big, requires height, and speed of response is slow, and viscosity is too high, brings certain difficulty to spinning, uses and receives very big restriction.The chemistry chain extension be meant in PA add chainextender can with the bifunctional or the polyfunctional group material of end group reaction; Is thereby that reacting environment reaches and increases the glutinous purpose that improves relative molecular mass with the forcing machine, it is as a kind of new sticking method that increases, and technical process is easy; Reaction is quick, and effect is better.In the chemistry chain extension, chainextender plays important effect.But so far, the chainextender that has occurred all is the further increases to the viscosity of PA product, and the purposes of industry report then only limits to the prepared in twin-screw extruder Polyamide Engineering Plastic; These chainextenders can not be applied in the polymeric amide direct polymerization technology; Extrude because the industriallization fiber mainly is single screw rod, add these chemical chainextenders after, react inhomogeneous and cause the material gel; Thereby make generation a large amount of waft silk and broken end, influence section spinning property in spinning.
Summary of the invention
technical problem to be solved by this invention is the deficiency that overcomes prior art; Provide a kind of chemical chain extension legal system to be equipped with polymeric amide and use chainextender; It not only can make an addition to and further improve the polymeric amide relative molecular mass in the polymeric amide; Also can be used in the direct polymerization technology of polymeric amide, directly obtain the polymeric amide of high molecular weight and good spinnability.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
a kind of chemical chain extension legal system is equipped with polymeric amide and uses chainextender; Said chainextender under 108 ℃～112 ℃ of temperature, reacts the multipolymer that made in 2～3 hours for polymethylmethacrylate and vinylbenzene are being equipped with stirrer, condensing surface and temperature control unit and are having in the stainless steel cauldron of nitrogen protection; The number-average molecular weight of said multipolymer is 6000～7500; Second-order transition temperature is 50 ℃～60 ℃, and wherein, the vinylbenzene weight percentage is 0.05%～2%.
Preferably, the density of said polymethylmethacrylate is 1.19kg/dm
3
, transmittance is 99%, shock strength>=16kg/cm
3
, tensile strength>=61kg/m
3
, thermal change type temperature>=78 ℃, thermal softening temperature>=105 ℃.
The another technical scheme that
the present invention takes is: a kind of chemical chain extension legal system is equipped with polymeric amide and uses chainextender; Said chainextender is for to be equipped with polymethylmethacrylate, vinylbenzene and maleic anhydride stirrer, condensing surface and temperature control unit and to have in the stainless steel cauldron of nitrogen protection; Under 108 ℃～112 ℃ of temperature, the multipolymer that reaction made in 2～3 hours, the number-average molecular weight of said multipolymer is 6000～7500; Second-order transition temperature is 50 ℃～60 ℃; Wherein, the vinylbenzene weight percentage is 0.05%～2%, and the weight percentage of maleic anhydride is 1% ~ 15%.
The present invention also can realize through following scheme: a kind of chemical chain extension legal system is equipped with polymeric amide and uses chainextender, the material of said chainextender for preparing through following steps:
(1), polymethylmethacrylate and vinylbenzene are being equipped with stirrer, condensing surface and temperature control unit and are having in the stainless steel cauldron of nitrogen protection; Under 108 ℃～112 ℃ of temperature; React and made multipolymer in 2～3 hours, this multipolymer number-average molecular weight is 6000～7500, and second-order transition temperature is 50 ℃～60 ℃; Wherein, the vinylbenzene weight percentage is 0.05%～2%;
(2), make step (1) gained multipolymer and epoxy resin at 120 ℃～180 ℃; Solvent is to react 1-3 (time) in the ETHYLE ACETATE to obtain described chainextender, and wherein the molar ratio of gained multipolymer and epoxy resin is 1:0.05～0.1.
According to the present invention, the density of above-mentioned polymethylmethacrylate is 1.19kg/dm
3
, transmittance is 99%, shock strength>=16kg/cm
3
, tensile strength>=61kg/m
3
, thermal change type temperature>=78 ℃, thermal softening temperature>=105 ℃.
the present invention also is particularly related to the purposes of above-mentioned chainextender in the direct polymerization technology of polycaprolactam.
When being used for such use, said chainextender being reinstated dissolution with solvents together with flowing agent one be made into chainextender
concentration is to add behind the solution of 2wt% ~ 15wt%, and the addition of this solution is 0.1% ~ 1% of a polycaprolactam weight.Preferably, flowing agent is Joncryl ADD 3310 products of BASF AG; Solvent is preferably PEG400, and the dissolved temperature is 87 ℃～93 ℃.
Because the enforcement of technique scheme, the present invention compared with prior art has following advantage:
chainextender provided by the invention not only is suitable for being added on and is used for further improving the polymeric amide relative molecular mass in the polymeric amide; Also can be used in the direct polymerization technology of polymeric amide; Directly obtain the polymeric amide of high molecular weight and good spinnability, the polycaprolactam section terminal amino group content that particularly adopts the direct polymerization technology of this chainextender to be obtained is stable, and dye uniformity is high in the post-treatment process; Good spinnability is fit to the production of polyamide fibre high-speed spinning and fine denier filament.
Description of drawings
Fig. 1 is the synoptic diagram that has shown the melting behaviour of embodiment 7,8 and common polycaprolactam;
Fig. 2 is the synoptic diagram that has shown the viscosity of embodiment 7,8 and common polycaprolactam;
Fig. 3 is the synoptic diagram that has shown embodiment 7,8 and common polycaprolactam tensile strength.
Embodiment
are done further detailed explanation below in conjunction with concrete embodiment to the present invention, but the invention is not restricted to following examples.
Embodiment 1
Chainextender according to present embodiment prepares through following steps: (density is 1.19kg/dm with the 10kg polymethylmethacrylate
3
, transmittance is 99%, shock strength>=16kg/cm
3
, tensile strength>=61kg/m
3
, thermal change type temperature>=78 ℃, thermal softening temperature>=105 ℃) and 0.1kg vinylbenzene stirrer, condensing surface and temperature control unit being housed and having in the stainless steel cauldron of nitrogen protection, under 110 ℃ of temperature, react and made multipolymer in 3 hours and be chainextender.
The physical property of
said chainextender is following: outward appearance is the transparent cake thing; Number-average molecular weight is 6200; Second-order transition temperature is 54 ℃; The vinylbenzene weight percentage is 0.7%.
Chainextender according to present embodiment prepares through following steps: (density is 1.19kg/dm with the 9kg polymethylmethacrylate
3
, transmittance is 99%, shock strength>=16kg/cm
3
, tensile strength>=61kg/m
3
, thermal change type temperature>=78 ℃, thermal softening temperature>=105 ℃) and 0.2kg vinylbenzene stirrer, condensing surface and temperature control unit being housed and having in the stainless steel cauldron of nitrogen protection, under 110 ℃ of temperature, react and made multipolymer in 2 hours and be chainextender.
The physical property of
said chainextender is following: outward appearance is the transparent cake thing; Number-average molecular weight is 6300; Second-order transition temperature is 54 ℃; The vinylbenzene weight percentage is 1.1%.
Embodiment 3
are according to the chainextender of present embodiment; Prepare through following steps: 8kg polymethylmethacrylate, 0.5kg vinylbenzene and 0.2kg maleic anhydride are being equipped with stirrer, condensing surface and temperature control unit and are having in the stainless steel cauldron of nitrogen protection; Under 110 ℃ of temperature, react and made multipolymer in 3 hours and be chainextender.
The physical property of
said chainextender is following: outward appearance is the transparent cake thing; Number-average molecular weight is 6700, and second-order transition temperature is 52 ℃, and wherein, the vinylbenzene weight percentage is 0.9%, and the weight percentage of maleic anhydride is 3%.
Chainextender according to present embodiment prepares through following steps:
(1), 8kg polymethylmethacrylate, 0.5kg vinylbenzene and 1kg maleic anhydride are being equipped with stirrer, condensing surface and temperature control unit and are having in the stainless steel cauldron of nitrogen protection; Under 110 ℃ of temperature; React and made multipolymer in 3 hours, recording number-average molecular weight is 6100.
(2), the bisphenol A type epoxy resin (viscosity is 12000mPas) of 8kg step (1) gained multipolymer and 0.5kg was reacted 2 hours in 150 ℃ of temperature, solvent ethyl acetate, obtain described chainextender.
The physical property of
said chainextender is following: outward appearance is the transparent cake thing; Number-average molecular weight is 7300, and second-order transition temperature is 53 ℃, and wherein, the vinylbenzene weight percentage is 0.48%, and the weight percentage of maleic anhydride is 8%
.
Embodiment 5
Present embodiment provides a kind of working method of polycaprolactam, and is specific as follows:
(1), 10kg embodiment 1 gained chainextender is joined among 90 ℃ the PEG400 with 0.5kg flowing agent (Joncryl ADD 3310 products of BASF AG), obtain chainextender concentration and be 5% solution.
(2), the hexanolactam after will purifying are pumped into first batch condensation polymerization reactor, and heating and temperature control is at 230～240 ℃; After 1 hour, be transported to second batch condensation polymerization reactor through melt pipe, in melt pipe, add various additives through injection nozzle through pump; 0.2% the chainextender that with weight is polycaprolactam weight injects through the A nozzle, and 0.3% hexanolactam injects through the B nozzle, and other additives inject at the C nozzle; As initiator, heating and temperature control is at 260～265 ℃, after 2 hours with water; Material is pumped into whole polycondensation vessel, and temperature is filtered through fondant filter at 240～250 ℃; Remove Cast Strip pelletizing, extraction, dry product behind the smelt gear pump, or go spinning behind the smelt gear pump.
Embodiment 6
present embodiment provides a kind of working method of polycaprolactam; Specific as follows: (1), 20kg embodiment 1 gained chainextender is joined among 90 ℃ the PEG400 with 2kg flowing agent (Joncryl ADD 3310 products of BASF AG) obtains chainextender concentration and is 10% solution.
(2), the hexanolactam after will purifying are pumped into first batch condensation polymerization reactor, and heating and temperature control is at 230～240 ℃; After 1 hour, be transported to second batch condensation polymerization reactor through melt pipe, in melt pipe, add various additives through injection nozzle through pump; 0.5% the chainextender that with weight is polycaprolactam weight injects through the A nozzle, and 0.3% hexanolactam injects through the B nozzle, and other additives inject at the C nozzle; As initiator, heating and temperature control is at 255～260 ℃, after 1 hour with water; Material is pumped into whole polycondensation vessel, and temperature is filtered through fondant filter at 235～240 ℃; Remove Cast Strip pelletizing, extraction, dry product behind the smelt gear pump, or go spinning behind the smelt gear pump.
Comparative Examples 1
this example provides a kind of direct polymerization technology of polycaprolactam, and specific as follows: the hexanolactam after will purifying is pumped into first batch condensation polymerization reactor; Heating and temperature control after 1 hour, is transported to second batch condensation polymerization reactor through pump through melt pipe at 230～240 ℃; In melt pipe, add various additives through injection nozzle, 0.3% hexanolactam injects through the B nozzle, and other additives inject at the C nozzle; As initiator, heating and temperature control is at 260～265 ℃, after 2 hours with water; Material is pumped into whole polycondensation vessel, and temperature is filtered through fondant filter at 240～250 ℃; Remove Cast Strip pelletizing, extraction, dry product behind the smelt gear pump, or go spinning behind the smelt gear pump.
are tested the physicals of the polycaprolactam of embodiment 5,6 and Comparative Examples 1; Wherein relative viscosity adopts the GB/T11832-93 test determines; Density adopts the GB1033-86 method to measure; Monomer content adopts S chromatogram internal mark method determination, and water cut adopts GB6509-86 to measure, and the result sees table 1.
The physical property of table 1 polycaprolactam
are visible from table 1, the polycaprolactam that has adopted the polymerization method of the chainextender of embodiment 1 to obtain, its relative viscosity with do not adopt chainextender that raising is by a relatively large margin arranged.In addition, though do not provide the effect data of embodiment 2,3 and 4, they all are on the basis of embodiment 1, to introduce maleic anhydride and further introduce epoxide group to prepare, and its effect is that those skilled in the art can expect.
Embodiment 7
Present embodiment provides a kind of embodiment 1 application of gained chainextender in the polycaprolactam injection moulding, and is specific as follows:
(1), 1kg embodiment 1 gained chainextender is joined among 90 ℃ the PEG400 with 0.05kg flowing agent (Joncryl ADD 3310 products of BASF AG), obtain chainextender concentration and be 5% solution.
(2), mix with 1kg step (1) gained solution through dried 4kg polyamide 6; These blends are under 230 ℃ of temperature; Compounding in the Brabender plasti-corder of 4 minutes residence time and 60 rev/mins; And forcing machine (WP30 millimeter dual-screw-stem machine, L/D=36) granulation are used in temperature and are 230 ℃ of injection moulding machine injection mouldings of operation down then.
Present embodiment provides a kind of embodiment 1 application of gained chainextender in the polycaprolactam injection moulding, and is specific as follows:
(1), with embodiment 7;
(2), mix with 2kg step (1) gained solution through dried 4kg polyamide 6; These blends are under 230 ℃ of temperature; Compounding in the Brabender plasti-corder of 4 minutes residence time and 60 rev/mins; And forcing machine (WP30 millimeter dual-screw-stem machine, L/D=36) granulation are used in temperature and are 230 ℃ of injection moulding machine injection mouldings of operation down then.
are not measured the polycaprolactam of embodiment 7 and 8 with adding moulded work rheological property and the mechanical property that chainextender of the present invention carries out the polycaprolactam of modification, the result is referring to Fig. 1～3.
are visible from Fig. 1～3, and chainextender of the present invention can significantly improve the viscosity and the tensile strength of polycaprolactam, and the amount of chainextender add many more, this raising effect is remarkable more.
Embodiment 9
present embodiment can improve the performance capability of the polycondensate resin of different series in order to explanation the present invention; 98.5 to 99.5 parts of mixtures that comprise 80% polybutylene terephthalate (from Yizheng petrochemical industry S31) and 20% polyamide 6 (from the B3 of BASF), dry back is done with the chainextender of 0.5% and 1% embodiment of the invention 1 and is mixed.Then, be used in 260 ℃ with 150 rev/mins of down forcing machines processing identical of operation with embodiment 1 employee.Rheological property after adopting capillary rheometer to different PBT/PA blend chain extensions is tested, and the result is referring to table 2.
The rheological property of PBT/PA blend contrast behind table 2 chain extension
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention
Claims (9)
1. a chemical chain extension legal system is equipped with polymeric amide and uses chainextender; It is characterized in that: said chainextender under 108 ℃～112 ℃ of temperature, reacts the multipolymer that made in 2～3 hours for polymethylmethacrylate and vinylbenzene are being equipped with stirrer, condensing surface and temperature control unit and are having in the stainless steel cauldron of nitrogen protection; The number-average molecular weight of said multipolymer is 6000～7500; Second-order transition temperature is 50 ℃～60 ℃, and wherein, the vinylbenzene weight percentage is 0.05%～2%.
2. chemical chain extension legal system according to claim 1 is equipped with polymeric amide and uses chainextender, it is characterized in that: the density of said polymethylmethacrylate is 1.19kg/dm
3, transmittance is 99%, shock strength>=16kg/cm
3, tensile strength>=61kg/m
3, thermal change type temperature>=78 ℃, thermal softening temperature>=105 ℃.
3. a chemical chain extension legal system is equipped with polymeric amide and uses chainextender; It is characterized in that: said chainextender is for to be equipped with polymethylmethacrylate, vinylbenzene and maleic anhydride stirrer, condensing surface and temperature control unit and to have in the stainless steel cauldron of nitrogen protection; Under 108 ℃～112 ℃ of temperature, the multipolymer that reaction made in 2～3 hours, the number-average molecular weight of said multipolymer is 6000～7500; Second-order transition temperature is 50 ℃～60 ℃; Wherein, the vinylbenzene weight percentage is 0.05%～2%, and the weight percentage of maleic anhydride is 1% ~ 15%.
4. chemical chain extension legal system according to claim 3 is equipped with polymeric amide and uses chainextender, it is characterized in that: the density of said polymethylmethacrylate is 1.19kg/dm
3, transmittance is 99%, shock strength>=16kg/cm
3, tensile strength>=61kg/m
3, thermal change type temperature>=78 ℃, thermal softening temperature>=105 ℃.
5. a chemical chain extension legal system is equipped with polymeric amide and uses chainextender, it is characterized in that: the material of said chainextender for preparing through following steps:
(1), polymethylmethacrylate and vinylbenzene are being equipped with stirrer, condensing surface and temperature control unit and are having in the stainless steel cauldron of nitrogen protection; Under 108 ℃～112 ℃ of temperature; React and made multipolymer in 2～3 hours, this multipolymer number-average molecular weight is 6000～7500, and second-order transition temperature is 50 ℃～60 ℃; Wherein, the vinylbenzene weight percentage is 0.05%～2%;
(2), make step (1) gained multipolymer and epoxy resin in 120 ℃～180 ℃ of temperature and solvent ethyl acetate, react and obtained described chainextender in 1～3 hour, wherein the molar ratio of multipolymer and epoxy resin is 1:0.05～0.1.
6. chemical chain extension legal system according to claim 5 is equipped with polymeric amide and uses chainextender, it is characterized in that: the density of said polymethylmethacrylate is 1.19kg/dm
3, transmittance is 99%, shock strength>=16kg/cm
3, tensile strength>=61kg/m
3, thermal change type temperature>=78 ℃, thermal softening temperature>=105 ℃.
7. the purposes of the described chainextender of each claim in the direct polymerization technology of polycaprolactam in the claim 1 to 6.
8. purposes according to claim 7 is characterized in that: said chainextender is reinstated dissolution with solvents together with flowing agent one, add after being made into the solution that chainextender concentration is 2wt%～15wt%, and the addition of this solution is 0.1%～1% of a polycaprolactam weight.
9. purposes according to claim 8 is characterized in that: said solvent is PEG400, and said being dissolved under 87 ℃～93 ℃ of the temperature carried out.
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| CN201110198573A CN102344564B (en) | 2011-07-15 | 2011-07-15 | Chain extender for polyamide preparation through chain extending |
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| CN103881001A (en) * | 2014-03-27 | 2014-06-25 | 杭州曦茂新材料科技有限公司 | Preparation method and application of comb-type epoxy capacity-increasing chain extender for polymer material |
| CN105297167A (en) * | 2015-11-24 | 2016-02-03 | 马海燕 | Large-diameter copolymerization polyamide monofilament and production method thereof |
| CN105859975A (en) * | 2016-06-19 | 2016-08-17 | 王金明 | Preparation method of capacity-increasing chain extender with core-shell structure |
| CN105859939A (en) * | 2016-06-20 | 2016-08-17 | 王金明 | Preparation method of organic silicon capacity increasing chain extender |
| CN105837722A (en) * | 2016-06-20 | 2016-08-10 | 王金明 | Preparation method of hydrophilic capacity-increasing chain extender |
| CN106188369A (en) * | 2016-07-28 | 2016-12-07 | 王金明 | A kind of preparation method of the chain-expanding agent containing organic fluorinated silicone |
| CN106065043B (en) * | 2016-07-28 | 2018-09-18 | 王金明 | A kind of preparation method of the Organic fluoride hydrophobic type chain extender containing ionic liquid |
| CN106400156B (en) * | 2016-08-31 | 2019-04-23 | 义乌华鼎锦纶股份有限公司 | A kind of preparation method of high-strength flatness nylon-6 fiber |
| CN108976783B (en) * | 2018-06-20 | 2020-04-10 | 上海锦湖日丽塑料有限公司 | Polyamide resin composition with high metal texture and preparation method thereof |
| CN109988263B (en) * | 2019-04-02 | 2021-12-28 | 嘉兴华雯化工股份有限公司 | Anhydride polymer chain extender and preparation method thereof |
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| CN101157739A (en) * | 2006-10-08 | 2008-04-09 | 周小雯 | Method for preparing macromolecule material chain extender |
| CN101338043A (en) * | 2007-07-02 | 2009-01-07 | 佛山市顺德区汉达精密电子科技有限公司 | Chain-expanding agent |
| GB2455738A (en) * | 2007-12-19 | 2009-06-24 | Ici Plc | Ethylenically unsaturated macromonomers |
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| 唐伟家."生物塑料用扩链剂".《塑料助剂》.2008,(第5期),24. |
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