CN103601887B - A kind of method of adding compound accelerant synthon level polyphenylene sulfide in stage casing - Google Patents
A kind of method of adding compound accelerant synthon level polyphenylene sulfide in stage casing Download PDFInfo
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- CN103601887B CN103601887B CN201310589924.5A CN201310589924A CN103601887B CN 103601887 B CN103601887 B CN 103601887B CN 201310589924 A CN201310589924 A CN 201310589924A CN 103601887 B CN103601887 B CN 103601887B
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Abstract
The invention discloses a kind of method of adding compound accelerant synthon level polyphenylene sulfide in stage casing, the method with santochlor and many water cure sodium for reaction raw materials synthesizes polyphenylene sulfide through polycondensation, add compound accelerant in the stage casing of reaction, described compound accelerant is lithium chloride, santochlor, trichloro-benzene and/or Meta Dichlorobenzene, N-Methyl pyrrolidone four kinds of components mix.Compared with prior art, method technique of the present invention is simple, and production cost is low, and the polyphenylene sulfide molecular weight of synthesis is high, the product lover of product, superior in quality.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of method of adding compound accelerant synthon level polyphenylene sulfide in stage casing.
Background technology
Polyphenylene sulfide is a kind of polymer novel material, and its english abbreviation is PPS.PPS has excellent thermotolerance, flame retardant resistance, the mechanics of erosion resistance and equilibrium and electric property and is all widely used at electronics, automobile, machinery and chemical field.
At present, the synthetic method of the comparatively ripe polyphenylene sulfide of domestic and international common use is all generally that synthesize polyphenylene sulfide through steps such as dehydration, polycondensations, the equation of reaction is as follows with santochlor and moisture sodium sulphite for reaction raw materials:
Above-mentioned method raw material easily obtains, but common processing method is difficult to the high molecular PPS resin being met service requirements.Even and synthesize under high-temperature and high-pressure conditions, also exist and be difficult to synthesize the defect of high molecular PPS, and because molecular weight is low, dispersity is high, the subsequent treatment process such as also need purified, hot oxygen crosslinked, just can reach service requirements.So, both extend production stage, added cost, and also made product colour deepen, affect the product phase of product.
In sum, existing PPS production technology is common exists synthesis technique complexity, processing condition require high, the growth of polymerization reaction late stage PPS molecular chain is not easy, be difficult to the PPS synthesizing high molecular (weight-average molecular weight is more than 40000), and the problem such as product colour is dark, quality is unstable.
Summary of the invention
The object of invention is the defect overcoming above-mentioned prior art, a kind of synthetic method of polyphenylene sulfide is provided, the method with the addition of compound accelerant in the reaction stage casing of santochlor and moisture sodium sulphite polycondensation, the polyphenylene sulfide of synthesis high molecular, product product lover, steady quality.
Technical scheme of the present invention is as follows:
A kind of method of adding compound accelerant synthon level polyphenylene sulfide in stage casing, the method with santochlor and many water cure sodium for reaction raw materials synthesizes polyphenylene sulfide through polycondensation, compound accelerant is added in the stage casing of reaction, described compound accelerant comprises A), B), C) three kinds of components, described A) component is santochlor, described B) component is trichloro-benzene and/or Meta Dichlorobenzene, described C) component is N-Methyl pyrrolidone.Above-mentioned compound accelerant can excite the activity of system, impels the chain length of the latter stage polyphenylene sulfide of reaction to increase, thus forms the PPS of macromolecule.
As preferred version of the present invention, A in above-mentioned compound accelerant), B), C) weight ratio of three kinds of components is (0.8 ~ 12): (0.5 ~ 5): (100 ~ 300).
As preferred version of the present invention, for improving the activity of reaction system further, promote that the chain length of the latter stage polyphenylene sulfide of reaction increases, described compound accelerant also comprises D) component, described D) component is lithium chloride.
As preferred version of the present invention, A in compound accelerant), B), C), D) weight ratio of four kinds of components is (0.8 ~ 12): (0.5 ~ 5): (100 ~ 300): (0 ~ 15).
As preferred version of the present invention, the consumption of compound accelerant is 0.2 ~ 12.5% of total supplementary material amount.
As preferred version of the present invention, compound accelerant adopts pressure differential method to drop in reactor.
As the further preferred version of the present invention, the pressure in reactor is 0.2 ~ 1.2mpa.
As preferred version of the present invention, with santochlor and many water cure sodium for reaction raw materials carries out polyreaction through the process point low-temperature zone of polycondensation synthesis polyphenylene sulfide, middle-temperature section, high temperature section, the temperature of reaction of low-temperature zone is 150 ~ 230 DEG C, the temperature of reaction of middle-temperature section is 231 ~ 240 DEG C, the temperature of reaction of high temperature section is 241 ~ 280 DEG C, and described compound accelerant drops at middle-temperature section.
As the further preferred version of the present invention, in low-temperature zone, many water cure sodium first dewaters under the effect of solvent and catalyzer, is then filled with nitrogen and reacts in airtight environment with santochlor.
Described solvent is N-Methyl pyrrolidone, and described catalyzer is lithium chloride
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention adds compound accelerant in the stage casing of polyreaction, and described compound accelerant can excite the activity of system, impels the chain length of the latter stage polyphenylene sulfide of reaction to increase, thus forms the PPS of macromolecule.
2, compound accelerant of the present invention adopts pressure differential method to be slowly pressed in reactor, without the need to decompression or cooling, reaction carried out continuously, increases substantially production efficiency.
3, polyreaction of the present invention adopts sectional temperature-controlled mode to carry out, and under the effect of low-temperature zone sodium sulphite at catalyzer, form active larger complex compound with solvent, then react with santochlor, speed of reaction is high; In addition, after adding compound accelerant, the activity of system raises, then heats up, and advantageously in the growth of polyphenylene sulfide chain length, promote the formation of the PPS of macromolecule, the molecular weight of the polyphenylene sulfide of synthesis is more than 40000.
4, method of the present invention is comparatively simple compared to existing technology, without the need to subsequent processing steps such as purifying, hot oxygen are cross-linked, simplifies production technique, can obtain again mutually high, the stay-in-grade PPS of product simultaneously.
Embodiment
Below by specific embodiment, the present invention is further described in detail, understands the claimed technical scheme of the present invention so that clear.
Embodiment 1
Low-temperature zone: in the reactor of 10 liters, adds Na
2s3H
2o1000g, catalyzer 380g and N-Methyl pyrrolidone 4200g carry out dehydration reaction; After dehydration, add santochlor 1200g, be filled with nitrogen, airtight, low temperature pre-polymerization 3h at the temperature of 220 DEG C.
Middle-temperature section: be warming up to 231 DEG C, uses pressure differential method to add compound accelerant 200g, and the pressure-controlling in reactor, in the scope of 0.40-0.9mpa, reacts 1.5h.
High temperature section: be finally warming up to 265 DEG C of reaction 3h, the pressure in reactor keeps the scope of 0.40-0.9mpa constant.
Above-mentioned catalyzer is lithium chloride.
Above-mentioned compound accelerant is santochlor, trichloro-benzene, N-Methyl pyrrolidone mix by weight for 0.8:0.5:100.
The polyphenylene sulfide uniform particles of final acquisition, particle diameter is 0.6-1.2mm, and unit weight reaches 400kg/m
3above, product colour is pure white, product lover, and weight-average molecular weight reaches more than 50000, and molecular weight distributing index is 2.0-2.3, superior in quality, can be directly used in spinning or other senior application.
Embodiment 2
Low-temperature zone: in the reactor of 10 liters, adds Na
2s3H
2o1000g, catalyzer 400g and N-Methyl pyrrolidone 3200g carry out dehydration reaction; After dehydration, add santochlor 1250g, be filled with nitrogen, airtight, low temperature pre-polymerization 2h at the temperature of 200 DEG C.
Middle-temperature section: be warming up to 240 DEG C, uses pressure differential method to add compound accelerant 250g, and the pressure-controlling in reactor, in the scope of 0.50-0.9mpa, reacts 1h.
High temperature section: be finally warming up to 255 DEG C of reaction 3h, the pressure in reactor keeps the scope of 0.50-0.9mpa constant.
Above-mentioned catalyzer is lithium chloride.
Above-mentioned compound accelerant is lithium chloride, santochlor, Meta Dichlorobenzene, N-Methyl pyrrolidone mix by weight for 15:12:5:300.
The polyphenylene sulfide uniform particles of final acquisition, particle diameter is 0.6-1.2mm, and unit weight reaches 400kg/m
3above, product colour is pure white, product lover, and weight-average molecular weight reaches more than 50000, and molecular weight distributing index is 2.0-2.3, superior in quality, can be directly used in spinning or other senior application.
Embodiment 3
Low-temperature zone: in the reactor of 10 liters, adds Na
2s3H
2o1000g, catalyzer 400g and N-Methyl pyrrolidone 3200g carry out dehydration reaction; After dehydration, add santochlor 1250g, be filled with nitrogen, airtight, low temperature pre-polymerization 2h at the temperature of 200 DEG C.
Middle-temperature section: be warming up to 240 DEG C, uses pressure differential method to add compound accelerant 250g, and the pressure-controlling in reactor, in the scope of 0.50-0.9mpa, reacts 1h.
High temperature section: be finally warming up to 255 DEG C of reaction 3h, the pressure in reactor keeps the scope of 0.50-0.9mpa constant.
Above-mentioned catalyzer is lithium chloride.
Above-mentioned compound accelerant is the mixing of lithium chloride, santochlor, Meta Dichlorobenzene and trichloro-benzene, N-Methyl pyrrolidone mixes by weight for 7:6:3:200.
The polyphenylene sulfide uniform particles of final acquisition, particle diameter is 0.6-1.2mm, and unit weight reaches 400kg/m
3above, product colour is pure white, product lover, and weight-average molecular weight reaches more than 50000, and molecular weight distributing index is 2.0-2.3, superior in quality, can be directly used in spinning or other senior application.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned embodiment and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (7)
1. one kind is added the method for compound accelerant synthon level polyphenylene sulfide in stage casing, the method with santochlor and many water cure sodium for reaction raw materials synthesizes polyphenylene sulfide through polycondensation, it is characterized in that: add compound accelerant in the stage casing of reaction, described compound accelerant comprises A), B), C) three kinds of components, described A) component is santochlor, described B) component is trichloro-benzene and/or Meta Dichlorobenzene, described C) component is N-Methyl pyrrolidone;
A in described compound accelerant), B), C) weight ratio of three kinds of components is (0.8 ~ 12): (0.5 ~ 5): (100 ~ 300);
Described compound accelerant adopts pressure differential method to drop in reactor;
Wherein, to be reaction raw materials carry out polyreaction through the process point low-temperature zone of polycondensation synthesis polyphenylene sulfide, middle-temperature section, high temperature section for dichlorobenzene and many water cure sodium, the temperature of reaction of low-temperature zone is 150 ~ 230 DEG C, the temperature of reaction of middle-temperature section is 231 ~ 240 DEG C, the temperature of reaction of high temperature section is 241 ~ 280 DEG C, and described compound accelerant in the reaction section drops into and refers to and to drop at middle-temperature section.
2. the method for compound accelerant synthon level polyphenylene sulfide is added in stage casing as claimed in claim 1, it is characterized in that: described compound accelerant also comprises D) component, described D) component is lithium chloride.
3. add as claimed in claim 2 the method for compound accelerant synthon level polyphenylene sulfide in stage casing, it is characterized in that: A in compound accelerant), B), C), D) weight ratio of four kinds of components is (0.8 ~ 12): (0.5 ~ 5): (100 ~ 300): (0 ~ 15).
4. the method for adding compound accelerant synthon level polyphenylene sulfide in stage casing as described in claims 1 to 3 any one, is characterized in that: the consumption of compound accelerant is 0.2 ~ 12.5% of total charging capacity.
5. add the method for compound accelerant synthon level polyphenylene sulfide as claimed in claim 4 in stage casing, it is characterized in that: the pressure in reactor is 0.2 ~ 1.2mpa.
6. the method for compound accelerant synthon level polyphenylene sulfide is added as claimed in claim 1 in stage casing, it is characterized in that: in low-temperature zone, many water cure sodium first dewaters under the effect of solvent and catalyzer, is then filled with nitrogen and reacts in airtight environment with santochlor.
7. add the method for compound accelerant synthon level polyphenylene sulfide as claimed in claim 6 in stage casing, it is characterized in that: described solvent is N-Methyl pyrrolidone, described catalyzer is lithium chloride.
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| CN107522861A (en) * | 2017-08-17 | 2017-12-29 | 四川金和成科技有限公司 | A kind of preparation method of film polyphenylene sulfide resin |
| CN107722274A (en) * | 2017-11-15 | 2018-02-23 | 天津工业大学 | A kind of preparation method of melt-blown polyphenylene sulfide |
| CN112480409A (en) * | 2020-12-03 | 2021-03-12 | 江苏优普生物化学科技股份有限公司 | Polyphenylene sulfide synthesis process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793202A (en) * | 2005-12-29 | 2006-06-28 | 四川得阳科技股份有限公司 | Tech., for polymerizing fibre grade polyphenyl sulfoether resin |
| CN103073720A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin |
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| JP4635344B2 (en) * | 2001-01-16 | 2011-02-23 | Ｄｉｃ株式会社 | Method for producing polyarylene sulfide resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793202A (en) * | 2005-12-29 | 2006-06-28 | 四川得阳科技股份有限公司 | Tech., for polymerizing fibre grade polyphenyl sulfoether resin |
| CN103073720A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin |
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Address after: Gaolan Port Economic Zone Fine Chemical District Lang Wan Lu 519050 Guangdong city of Zhuhai Province Patentee after: Zhuhai Changxian New Materials Technology Co., Ltd. Address before: Gaolan Port Economic Zone Fine Chemical District Lang Wan Lu 519050 Guangdong city of Zhuhai Province Patentee before: Zhuhai Changxian Chemical Technology Co., Ltd. |