Fiber grade polyphenylene sulfide resin synthesis method

Patent metadata

Field	Value
Publication number	US-9567440-B2
Application number	US-201314655326-A
Country	US
Kind code	B2
Filing date	Oct 29, 2013
Priority date	Dec 26, 2012
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

The present invention discloses a fiber-grade polyphenylene sulfide resin synthesis method, taking sodium bisulfide and p-dichlorobenzene as raw materials, N-methyl pyrrolidone as the solvent and C5-C6 fatty acid salt formed through dehydration to C5-C6 fatty acid and sodium hydroxide as the polymerization additive for synthesis through polymerization. White polyphenylene sulfide resin is obtained through acidification and washing of reaction slurry. In view of the fact that MFR is below 125 g/10 min, weight-average molecular weight as measured by GPC is over 4.2×10 4 , and whiteness is over 90, it can satisfy requirements for fiber polyphenylene sulfide resin. C5-C6 fatty acid salt according to the method of the present invention has a higher solubility in NMP, which can better promote polymerization. It is to be fully diverted into the filtrate after filter prior to conversion into free fatty acid again through acidification with hydrochloric acid. C5-C6 fatty acid is available for azeotropy with water, which has a limited solubility in water. Therefore, it is applicable to recycle C5-C6 fatty acid from the filtrate through azeotropy with water, and thereby solve the problem with separation of additive and sodium chloride that are soluble in water.

First claim

The invention claimed is:

1. A fiber-grade polyphenylene sulfide resin synthesis method, characterized in that the method uses sodium bisulfide and p-dichlorobenzene as raw materials, N-methyl pyrrolidone as a solvent and C5-C6 fatty acid salt as a polymerization additive for synthesis through polymerization, characterized further in that the C5-C6 fatty acid salt is C5-C6 fatty acid sodium salt, and characterized further in the following reaction steps:
(1) adding NMP, 40%-50% NaOH solution and C5-C6 fatty acid into the reactor for heating to the temperature of 90-120° C. simultaneously with mixing and nitrogen protection at the velocity of 1.0˜2.0° C./min; proceeding with heat preservation for 1-3 hours before prior to further heating to temperature of 180˜200° C. at the velocity of 1.0˜2.0° C./min for dehydration; reducing temperature to 110˜130° C. after dehydration;
(2) adding NaHS solution and NMP into the reactor following Step (1) for heating to temperature of 180˜200° C. at the velocity of 0.7˜1.5° C./min simultaneously with mixing and nitrogen protection prior to dehydration; further reducing temperature to 140˜160° C. when water content in the system is below 1.0 mol/mol sulfur;
(3) adding PDCB and NMP into the reactor following Step (2) for heating to the temperature of 220˜240° C. within 1.0-1.5 hours prior to heat preservation for 1-3 hours; further proceeding with heating to temperature of 260˜280° C. at the velocity of 1.0˜1.5° C./min prior to heat preservation for 1-3 hours; once completed, reducing temperature to 130˜150° C. within 0.5-1 hour to obtain PPS reaction slurry;
(4) proceeding with centrifugation of PPS reaction slurry as obtained through Step (3), then leaching with 130˜150° C. NMP of the same mass as the filter cake; further proceeding with leaching with hydrochloric acid solution of the same mass as the filter cake prior to mixing and collection of all filtrate;
(5) repeatedly washing the filter cake as obtained in Step (4) with 70˜100° C. deionized water; further drying the filter cake to obtain polyphenylene sulfide resin.

2. The fiber-grade polyphenylene sulfide resin synthesis method according to claim 1 , characterized in that 1.0 mol NaHS is selected as the benchmark for materials used in reaction step (1); total consumption of C5-C6 fatty acid, NMP and NaOH is up to 0.1˜0.5 mol, 2.8˜3.2 mol and 1.1˜1.5 mol respectively.

3. The fiber-grade polyphenylene sulfide resin synthesis method according to claim 1 , characterized in that 1.0 mol NaHS is selected as the benchmark for materials used in reaction step (2); total NMP in the system is 3.2˜3.6 mol after addition of NaHS and NMP.

4. The fiber-grade polyphenylene sulfide resin synthesis method according to claim 1 , characterized in that 1.0 mol NaHS is selected as the benchmark for materials used in reaction step (3); consumption of PDCB and total NMP in the system is up to 0.99˜1.02 mol and 4.3˜4.7 mol respectively after addition of PDCB and NMP.

5. The fiber-grade polyphenylene sulfide resin synthesis method according to claim 1 , characterized in that 1.0 mol polymerization additive is selected as the benchmark for leaching with hydrochloric acid in the said Step (4); consumption of hydrochloric acid is 1.2˜1.3 mol.

6. The fiber-grade polyphenylene sulfide resin synthesis method according to claim 1 , characterized in that the filtrate as obtained in Step (4) is to be agitated and mixed for separation of C5-C6 fatty acid through azeotropic rectification in the rectification device with water separator; proceed with further rectification to remove the moisture; finally, proceeding with depressurized distillation for recycling of solvent NMP.

7. The fiber-grade polyphenylene sulfide resin synthesis method according to claim 1 , characterized in that the C5-C6 fatty acid salt is generated through reaction among hexanoic acid, pentanoic acid, isovleric acid, 2-ethyl butyric acid and their mixture of random proportion as well as alkali.

Assignees

• Zhejiang Nhu Special Mat Co Ltd
• Univ Zhejiang
• Shangyu Nhu Biological Chemical Co Ltd
• Zhejiang Nhu Co Ltd

Inventors

• Chen Zhirong
• Li Woyuan
• Li Haoran
• Lian Ming
• Yin Hong
• Zhou Guiyang
• Zheng Xinfeng

Classifications

• C08G75/02

  Polythioethers · CPC title

• C08G75/16 Primary

  by polycondensation of organic compounds with inorganic polysulfides · CPC title