CN100354361C - Method for lowering melting point of fusible polyacrylonitrile resin - Google Patents
Method for lowering melting point of fusible polyacrylonitrile resin Download PDFInfo
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- CN100354361C CN100354361C CNB2004100532334A CN200410053233A CN100354361C CN 100354361 C CN100354361 C CN 100354361C CN B2004100532334 A CNB2004100532334 A CN B2004100532334A CN 200410053233 A CN200410053233 A CN 200410053233A CN 100354361 C CN100354361 C CN 100354361C
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- polyacrylonitrile resin
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- fusing point
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Abstract
The present invention relates to a method for lowering the melting point of fusible polyacrylonitrile resin. In the method, a solid additive and fusible polyacrylonitrile resin granules are mixed to form a homogeneous mixture by machinery, wherein the additive is taken from one of a para-hydroxybenzoic acid or an isophthalic acid, or a mixture of the para-hydroxybenzoic acid and the isophthalic acid. The mixed weight ratio of the additive to the polyacrylonitrile resin is 1: (10 to 40), and the additive is powder or fine granules with granularity smaller than 200 meshes. The method provided by the present invention has a simple manufacturing process, which can lower the melting point of the fusible polyacrylonitrile resin to be below 200 DEG C and thoroughly avoid fusible polyacrylonitrile from possible decomposition in a melting process. The method can obviously increase the melt index of the resin and improve the flow property of fused masses simultaneously, and is favorable to increase the processing performance of the resin.
Description
Technical field
The present invention relates to reduce the method for fusible polyacrylonitrile resin fusing point, particularly a kind of method that reduces the fusible polyacrylonitrile resin fusing point by the adding solid additive.
Background technology
Polyacrylonitrile resin is the wider superpolymer of a kind of purposes, particularly adopts the fibre property of acrylic resin manufacturing to exactly like wool, occupies very big proportion in the synthon production.But a defective of polyacrylonitrile resin is a fusing point (theoretical value is 319 ℃) is higher than decomposition temperature (being generally 250 ℃), therefore it can't be processed with the fused method, polyacrylonitrile fibre also can only be used the method manufacturing of solvent spinning usually, this spinning processes will use a large amount of poisonous and harmfuls or mordant solvent, must carry out the recovery and the purification of solvent in process of production, and must wash and drying etc. fiber, so complex process and environmental pollution are serious.
For many years, reduce the research of polyacrylonitrile fusing point and quite paid close attention to, and obtained gratifying progress.In prior art, more in the past is to adopt the water plasticising method of (comprising low molecular solvent plasticising), water or other low molecular solvent can make this mixture be molten state under lower temperature after polyacrylonitrile resin is soaked into, but when adopting this kind method to carry out melt-spinning, easily produce cavity filament, fracture of wire, lousiness, fiber also can exist internal capillary and surface imperfection, thereby causes fibre property to descend greatly, so also there is more problem in suitability for industrialized production.
Become the focus of exploitation fusible polyacrylonitrile resin in recent years as internally plasticized chemical modification method, it is to introduce the comonomer that can form flexible chain on the polyacrylonitrile macromolecular chain, thereby reduce the fusing point of polyacrylonitrile, make fusible polyacrylonitrile resin.This comonomer mainly comprises methyl methacrylate and methacrylonitrile, and the crotononitrile that proposed of Chinese patent application 02136955.0.The fusible polyacrylonitrile resin that obtains by chemical modification method should belong to fusible polyacrylonitrile resin truly.But, existing fusible polyacrylonitrile resin fusing point is generally all between 200 ℃ to 250 ℃, yet studies show that, be subjected to the different molecule regularities and the influence of different molecular weight, when temperature during near 200 ℃ the polyacrylonitrile molecule existed part to decompose, so the optimal processing fusing point of fusible polyacrylonitrile resin is to be lower than 200 ℃.Although can further reduce the fusing point of fusible polyacrylonitrile resin by the content that increases comonomer, but too high content can have influence on the original proterties of polyacrylonitrile, will change the original style of polyacrylonitrile fibre with the fiber of this polyacrylonitrile resin manufacturing.
Summary of the invention
The invention provides a kind of method that reduces the fusible polyacrylonitrile resin fusing point, the technical problem that it will solve is by add a kind of solid-state additive in existing fusible polyacrylonitrile resin, the processing fusing point of fusible polyacrylonitrile resin is reduced to below 200 ℃, and the additive that adds can not produce detrimentally affect when polyacrylonitrile resin carries out melt-processed and to the product performance that make.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of method that reduces the fusible polyacrylonitrile resin fusing point, this method comprises a kind of solid-state additive and fusible polyacrylonitrile resin particle is formed uniform mixture by mechanically mixing, additive is taken from a kind of in P-hydroxybenzoic acid or the m-phthalic acid, or is both mixture.Additive and polyacrylonitrile resin blended weight ratio are additive: polyacrylonitrile resin=1: 10～1: 40, additive are that granularity is less than 200 purpose powder or fine particles.
Above-mentioned additive is preferably P-hydroxybenzoic acid; Additive and polyacrylonitrile resin blended weight ratio are preferably additive: polyacrylonitrile resin=1: 10～1: 25.
Above-mentioned fusible polyacrylonitrile resin is the multipolymer that the vinyl cyanide and the second copolymerization units copolymerization form, second copolymerization units can be methyl methacrylate, methacrylonitrile or crotononitrile, is that the content of benchmark second copolymerization units in multipolymer is 10～18 weight % with the total amount of all polymerized units.
The viscosity-average molecular weight of polyacrylonitrile resin generally can be 20000～60000 in the technique scheme.
Polyacrylonitrile resin then no longer needs other to improve the second flexible monomer the multipolymer as being used for making polyacrylonitrile fibre, but in order to obtain good dyeing behavior, the 3rd monomer that is used for dyeing, modifying will need.Therefore, also can contain the 3rd copolymerization units methylpropene sodium sulfonate in the above-mentioned polyacrylonitrile resin, methylpropene sodium sulfonate is that the content of benchmark is 0.2～1.0 weight % with the total amount of all polymerized units.
Analyze from principle, technical scheme provided by the invention also do not require and limits the concrete kind of second copolymerization units that makes polyacrylonitrile reduce fusing point, more than these second copolymerization units only be that the contriver recommends.The known in fact this copolymerization units with same function has also comprised the monomeric multipolymer of other unsaturated olefin, as being vinylformic acid, esters of acrylic acid and derivative thereof; Toxilic acid (maleic anhydride), maleic acid ester class and derivative thereof; Propene sulfonic acid, propene sulfonic acid salt and derivative thereof; Haloalkene hydro carbons, acrylamide and derivative thereof; Styrenic and vinyl esters organism or the like.Those skilled in the art can know the technical program by inference and be applied to also will obtain identical effect by the fusible polyacrylonitrile resin that other similar copolymerization units and acrylonitrile compolymer obtain.
We know why polyacrylonitrile resin has high melt point is that therefore the interaction force of weakening-CN group just can reduce the fusing point of polyacrylonitrile resin because contain strong polar group-CN in its molecular chain.The additive that the present invention adopts is a kind of compound that contains hydrogen bond, the contriver found through experiments this compound and can weaken greatly-interaction force of CN group, and weaken cyclic action between adjacent-CN group, thereby can reduce the fusing point of polyacrylonitrile significantly.And because this additive is that granularity is less than 200 purpose powder or fine particles, it will be evenly distributed in the melt after the polyacrylonitrile resin fusion, unlike adopting water or low molecular solvent plasticising to reduce the method for polyacrylonitrile resin fusing point, because of the evaporation of water or solvent will cause having bubble in the melt, thereby finally influence the mechanical property of resin such as fiber.
The fusing point of fusible polyacrylonitrile resin is downward trend with the increase of additive add-on, and the contriver found through experiments additive and polyacrylonitrile resin blended weight ratio is proper in 1: 10～1: 40 scope.The additive reduction of fusing point after a little while is not obvious, with the physicals of impact polypropylene nitrile resin, all can produce in various degree influence to spinning property and quality of fiber especially when resin is used to make fiber when additive is too much.
Compared with prior art, the processing fusing point that positive effect of the present invention has been to provide the simple method of a kind of technology to make fusible polyacrylonitrile resin is reduced to below 200 ℃, has thoroughly avoided fusible polyacrylonitrile issuable decomposition in the melt-processed process.Because the melting index of resin obviously improves, the flowing property of melt also improves simultaneously, and this is highly beneficial to the processing characteristics that improves resin.
Below will the invention will be further described by specific embodiment.
Embodiment
Fusing point adopts the sensible heat analysis-e/or determining among the embodiment, temperature rise rate: 3 ℃/minute is fusing point with the temperature during the whole fusion of polymkeric substance on the instrument; Melting index adopts the melt flow rate (MFR) instrument to measure, mouthful mould: diameter 2.095mm, length 8mm; Viscosity-average molecular weight adopts Ubbelohde viscometer to measure specific viscosity η sp, obtains by conversion then.
[embodiment 1]
Get fusible polyacrylonitrile resin and additive and join in the open container that whipping appts 2L is housed by required weight ratio, stir about 15min, even until additive and mixed with resin.Additive is crushed to Powdered additive or fine particulate earlier as there being bulk, requires granularity to be no more than 200 orders.
Fusible polyacrylonitrile resin is the multipolymer of vinyl cyanide and methyl methacrylate, total amount with all polymerized units is that the content of benchmark methyl methacrylate in multipolymer is 15 weight %, the viscosity-average molecular weight of resin is 4000, the fusing point of resin is 240 ℃, and 240 ℃ of melting index that record are the 11g/10 branch.
[embodiment 2～8]
Fusible polyacrylonitrile resin is the multipolymer of vinyl cyanide and crotononitrile, is that the content of benchmark crotononitrile in multipolymer is 14 weight % with the total amount of all polymerized units, and the viscosity-average molecular weight of polyacrylonitrile resin is 3500.All the other are with embodiment 1
It is 1 listed that concrete additive, additive and the polyacrylonitrile resin blended weight ratio that adopts of each embodiment, the fusing point of mixture and melting index see Table.
Further the low melting point fusible polyacrylonitrile resin that obtains with embodiment 2～8 is a raw material, adopts the technology of melt-spinning to carry out spinning, makes the acrylic fiber of 1.46dtex, the breaking tenacity and the extension at break of test fiber, and it the results are shown in Table 2.
Table 1.
| Additive | Additive/resin (weight ratio) | Fusing point (℃) | Melting index (g/10min) | |
| Embodiment 1 | P-hydroxybenzoic acid | 1/18 | 191 | 29.2 |
| Embodiment 2 | P-hydroxybenzoic acid | 1/10 | 160 | 47.3 |
| Embodiment 3 | P-hydroxybenzoic acid | 1/15 | 180 | 33.4 |
| Embodiment 4 | P-hydroxybenzoic acid | 1/25 | 196 | 24.6 |
| Embodiment 5 | P-hydroxybenzoic acid | 1/40 | 200 | 14.0 |
| Embodiment 6 | M-phthalic acid | 1/10 | 180 | 36.3 |
| Embodiment 7 | M-phthalic acid | 1/15 | 195 | 19.7 |
| Embodiment 8 | M-phthalic acid | 1/20 | 200 | 17.6 |
Table 2.
| Breaking tenacity (CN/dtex) | Extension at break (%) | |
| Embodiment 2 | 3.0 | 28 |
| Embodiment 3 | 3.4 | 23 |
| Embodiment 4 | 3.9 | 19 |
| Embodiment 5 | 4.1 | 17 |
| Embodiment 6 | 2.8 | 29 |
| Embodiment 7 | 3.0 | 27 |
| Embodiment 8 | 3.2 | 24 |
Claims (6)
1, a kind of method that reduces the fusible polyacrylonitrile resin fusing point, this method comprises a kind of solid-state additive and fusible polyacrylonitrile resin particle is formed uniform mixture by mechanically mixing, additive is taken from a kind of in P-hydroxybenzoic acid or the m-phthalic acid, or be both mixture, additive and polyacrylonitrile resin blended weight ratio are additive: polyacrylonitrile resin=1: 10～1: 40, additive are that granularity is less than 200 purpose powder or fine particles.
2, the method for reduction fusible polyacrylonitrile resin fusing point according to claim 1 is characterized in that at described additive be P-hydroxybenzoic acid.
3, the method for reduction fusible polyacrylonitrile resin fusing point according to claim 1 is characterized in that at described additive and polyacrylonitrile resin blended weight ratio be additive: polyacrylonitrile resin=1: 10～1: 25.
4, the method for reduction fusible polyacrylonitrile resin fusing point according to claim 1, it is characterized in that described fusible polyacrylonitrile resin is the multipolymer that the vinyl cyanide and the second copolymerization units copolymerization form, second copolymerization units is methyl methacrylate, methacrylonitrile or crotononitrile, is that the content of benchmark second copolymerization units in multipolymer is 10～18 weight % with the total amount of all polymerized units.
5, according to the method for claim 1,2,3 or 4 described reduction fusible polyacrylonitrile resin fusing points, the viscosity-average molecular weight that it is characterized in that described polyacrylonitrile resin is 20000～60000.
6, according to the method for claim 1,2,3 or 4 described reduction fusible polyacrylonitrile resin fusing points, it is characterized in that containing in described polyacrylonitrile resin the 3rd copolymerization units methylpropene sodium sulfonate, is that the content of methylpropene sodium sulfonate in the benchmark multipolymer is 0.2～1.0 weight % with the total amount of all polymerized units.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100532334A CN100354361C (en) | 2004-07-29 | 2004-07-29 | Method for lowering melting point of fusible polyacrylonitrile resin |
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| CNB2004100532334A CN100354361C (en) | 2004-07-29 | 2004-07-29 | Method for lowering melting point of fusible polyacrylonitrile resin |
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| CN100354361C true CN100354361C (en) | 2007-12-12 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03176196A (en) * | 1989-12-06 | 1991-07-31 | Ricoh Co Ltd | Thermal transfer recording medium |
| EP0629729A1 (en) * | 1993-06-17 | 1994-12-21 | The Standard Oil Company | Nonwoven fabrics from high nitrile copolymers |
| CN1107166A (en) * | 1993-11-10 | 1995-08-23 | 标准石油公司 | A process for making a polymer of acrylonitrie, methacrylonitrile and olefinically unsaturated monomers |
| WO2000050509A1 (en) * | 1999-02-22 | 2000-08-31 | The Standard Oil Company | Lubricants for melt processable multipolymers of acrylonitrile and olefinically unsaturated monomers |
| CN1465648A (en) * | 2002-06-17 | 2004-01-07 | 中国人民解放军第二军医大学 | Phase change energy storage composite material and preparation process thereof |
| CN1482149A (en) * | 2002-09-12 | 2004-03-17 | 中国石化上海石油化工股份有限公司 | Fusible polyacrylonitrile resin |
-
2004
- 2004-07-29 CN CNB2004100532334A patent/CN100354361C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03176196A (en) * | 1989-12-06 | 1991-07-31 | Ricoh Co Ltd | Thermal transfer recording medium |
| EP0629729A1 (en) * | 1993-06-17 | 1994-12-21 | The Standard Oil Company | Nonwoven fabrics from high nitrile copolymers |
| CN1107166A (en) * | 1993-11-10 | 1995-08-23 | 标准石油公司 | A process for making a polymer of acrylonitrie, methacrylonitrile and olefinically unsaturated monomers |
| WO2000050509A1 (en) * | 1999-02-22 | 2000-08-31 | The Standard Oil Company | Lubricants for melt processable multipolymers of acrylonitrile and olefinically unsaturated monomers |
| CN1465648A (en) * | 2002-06-17 | 2004-01-07 | 中国人民解放军第二军医大学 | Phase change energy storage composite material and preparation process thereof |
| CN1482149A (en) * | 2002-09-12 | 2004-03-17 | 中国石化上海石油化工股份有限公司 | Fusible polyacrylonitrile resin |
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Granted publication date: 20071212 Termination date: 20110729 |