CN110760021A - Vinyl chloride polymerization terminator with good low-temperature fluidity, and preparation method and application thereof - Google Patents
Vinyl chloride polymerization terminator with good low-temperature fluidity, and preparation method and application thereof Download PDFInfo
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- CN110760021A CN110760021A CN201810823006.7A CN201810823006A CN110760021A CN 110760021 A CN110760021 A CN 110760021A CN 201810823006 A CN201810823006 A CN 201810823006A CN 110760021 A CN110760021 A CN 110760021A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
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- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention belongs to the field of resin synthesis, and particularly relates to a vinyl chloride polymerization terminator with good low-temperature fluidity, and a preparation method and application thereof. The paint comprises the following components in parts by weight: 20-30 parts of diethylhydroxylamine; 30-40 parts of ethylene glycol diglycidyl ether; 20-30 parts of diphenyl isodecyl phosphite; 40-50 parts of deionized water and 0.5-2 parts of a dispersing agent. The dispersing agent is a polyvinyl alcohol aqueous solution with polymerization degree of 300-400, alcoholysis degree of 50-60% and concentration of 5%. The terminator of the invention has good low-temperature fluidity, is suitable for being applied to areas or seasons with lower temperature, can keep the uniformity and stability of the composite terminator without adding an emulsifier, and also provides a preparation method and application thereof, which not only can play a good vinyl chloride polymerization termination effect and improve the thermal stability of resin, but also has excellent low-temperature fluidity so as to be convenient for being used in cold areas or seasons.
Description
Technical Field
The invention belongs to the field of resin synthesis, and particularly relates to a vinyl chloride polymerization terminator with good low-temperature fluidity, and a preparation method and application thereof.
Background
The terminating agent stops or significantly reduces the reaction rate by combining with residual initiator reactive radicals and residual initiator to form inactive compounds, which effectively protects the polymer from damage by thermal oxygen aging during stripping and subsequent processing. The terminator is added when the polymerization reaction reaches a set end point, and commonly used terminators are bisphenol A, thiosemicarbazone, BHT, and the like. A single terminator often cannot meet the requirements of efficiently terminating the polymerization reaction and improving the thermal stability of the resin at the same time, and the terminator is developing towards the functional compound direction of both chain termination and improving the thermal stability of PVC.
CN201110380532 discloses a preparation method and a use method of a polyvinyl chloride resin terminator, wherein the terminator is an oil-soluble composite liquid terminator and is mainly compounded by HKY-10, a benzofuranone antioxidant and a phosphite antioxidant. The liquid antioxidant is prepared by dissolving 2, 6-di-tert-butyl-4- (1-phenylethyl) phenol in an organic solvent, the aging whiteness of PVC resin products can be improved by using the terminator, and the terminator introduces the organic solvent and can potentially influence the production and polymerization of PVC.
CN103435725A discloses an aqueous emulsion type polyvinyl chloride resin terminator and a preparation method thereof, wherein the terminator comprises, by weight, 70-140 parts of a stabilizer, 18-42 parts of a phenol antioxidant, 0.1-0.3 part of a light stabilizer, 4-18 parts of a polymerization inhibitor, 13-96 parts of an emulsifier, 1-8 parts of a dispersant, and 100-320 parts of water, the stabilizer and the phenol antioxidant are placed in a stirrer to be heated and dissolved, the temperature is reduced to normal temperature after heat preservation, then the light stabilizer and the polymerization inhibitor are added, and the mixture is stirred uniformly to obtain a mixed terminator solution. And adding an emulsifier into the mixed terminator solution, heating to 40-60 ℃, uniformly stirring, and mixing the emulsion. And simultaneously mixing the dispersing agent and water, stirring and heating to 80-100 ℃ to obtain a dispersing solution. And finally, adding the dispersion solution into the mixed emulsion to obtain the aqueous emulsion type polyvinyl chloride terminator. The aqueous emulsion type terminator can well improve the thermal stability and the processing performance of PVC resin while terminating polymerization, and the phenolic antioxidant used by the invention is toxic.
CN106749794 discloses a polymerization method for reducing resin fish eyes, which comprises the steps of adding deionized water, vinyl chloride monomer, composite dispersant, anti-fish eye agent, composite initiator and stabilizer into a polymerization kettle for polymerization, wherein the polymerization pressure is 1.0-1.1 MPa, the polymerization temperature is 52-60 ℃, and adding a terminator diethylhydroxylamine when the polymerization pressure is reduced to 0.05-0.09 MPa. The polymerization method reduces the fish eye number of the PVC resin and improves the aging whiteness of the resin. Although the invention also uses ethylene glycol diglycidyl ether and diethylhydroxylamine, the adding mode and the effect are different from the patent, and the effect is different, which is mainly represented in the following three aspects: 1. the patent uses a single diethylhydroxylamine terminator, but the invention uses a compound terminator of diethylhydroxylamine and ethylene glycol diglycidyl ether (the patent uses a single diethylhydroxylamine terminator, the thermal stability of the resin can not be improved.2. the patent adds ethylene glycol diglycidyl ether at the beginning of polymerization, the ethylene glycol diglycidyl ether and diethylhydroxylamine of the patent are firstly compounded into the compound terminator, the patent adds the ethylene glycol diglycidyl ether at the beginning of polymerization and consumes the polymerization initiator, and reduces the polymerization reaction rate.3. the ethylene glycol diglycidyl ether of the patent only plays a role in thermal stability of PVC resin, and the ethylene glycol diglycidyl ether of the patent not only can keep better fluidity at low temperature by compounding with diethylhydroxylamine and diphenyl-isodecyl phosphite, the method also has the effects of synergistically stopping polymerization and improving the whiteness of the resin, and the aged resin prepared by the method has higher whiteness. Therefore, the effects are different.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a vinyl chloride polymerization terminator with good low-temperature fluidity, which is suitable for being applied to areas or seasons with low air temperature, has uniform and stable components, can rapidly terminate polymerization reaction and endows PVC resin with higher aging whiteness, and also provides a preparation method and application thereof.
The vinyl chloride polymerization terminator with good low-temperature fluidity comprises the following components in parts by weight:
20-30 parts of diethylhydroxylamine; 30-40 parts of ethylene glycol diglycidyl ether; 20-30 parts of diphenyl isodecyl phosphite; 40-50 parts of deionized water and 0.5-2 parts of a dispersing agent.
The dispersing agent is polyvinyl alcohol aqueous solution with polymerization degree of 300-400, alcoholysis degree of 50-60% and concentration of 3-6%, and the concentration is preferably 5%.
The preparation method of the vinyl chloride polymerization terminator with good low-temperature fluidity comprises the following steps: the method comprises the following steps: all the components are put into a glass beaker to be mixed and stirred, and then are added into a high-speed shearing emulsifying machine to be emulsified, so that the vinyl chloride polymerization terminator with good low-temperature fluidity is obtained.
Wherein: the mixing and stirring time is 10-20 min.
Adding the mixture into a high-speed shearing emulsifying machine to emulsify for 20-30 min at the rotating speed of 1500-3000 r/min.
The application of the vinyl chloride polymerization terminator with good low-temperature fluidity comprises the steps of adding desalted water, a polyvinyl alcohol PVA80 aqueous solution, a hydroxypropyl methyl cellulose E50 aqueous solution, tert-butyl peroxyneodecanoate and tert-amyl peroxypivalate into a reaction kettle, pumping the pressure in the kettle to be lower than-0.09 MPa, adding vinyl chloride monomer, starting stirring, stirring and mixing at normal temperature, heating, reacting, and adding the vinyl chloride polymerization terminator with good low-temperature fluidity into the kettle when the pressure in the kettle is reduced by 0.25-0.35 MPa.
Preferably, the reaction kettle is a 5L stainless steel pressure reaction kettle provided with two layers of double-blade flat slurry.
Preferably, vinyl chloride monomer is added, stirring is started, the rotating speed is controlled to be 440-470 rpm, stirring and mixing are carried out for 10-15 min at normal temperature, then the temperature is raised to 58.0 +/-0.2 ℃, the reaction is started for timing after the temperature is stabilized, and when the pressure in the kettle is reduced by 0.25-0.35 MPa, the vinyl chloride polymerization terminator with good low-temperature fluidity is added into the kettle.
As a preferable technical scheme, the application of the vinyl chloride polymerization terminator with good low-temperature fluidity comprises the steps of adding 1.8-2.4 kg of desalted water, 8-10 g of a 5% polyvinyl alcohol PVA80 aqueous solution, 6.3-6.5 g of a 3% hydroxypropyl methyl cellulose E50 aqueous solution, 0.255-0.267 g of 75% tert-butyl peroxyneodecanoate and 0.500-0.533 g of 75% tert-amyl peroxypivalate into a reaction kettle, pumping the pressure in the kettle to be lower than-0.09 MPa, adding 1kg of vinyl chloride monomer, starting stirring, controlling the rotation speed to be 440-470 rpm, stirring and mixing for 10-15 min at normal temperature, raising the temperature of the kettle to 58.0 +/-0.2 ℃, starting reaction timing after the temperature is stabilized, and adding the vinyl chloride polymerization terminator with good low-temperature fluidity into the kettle when the pressure in the kettle is reduced by 0.25-0.35 MPa.
The addition amount of the vinyl chloride polymerization terminator with good low-temperature fluidity is 400-800 ppm based on the weight of vinyl chloride.
Compared with the prior art, the invention has the following advantages:
(1) the composite terminator consisting of the diethylhydroxylamine, the diphenyl-isodecyl phosphite and the ethylene glycol diglycidyl ether has good low-temperature fluidity, is suitable for being applied to areas or seasons with low air temperature, has uniform and stable components, can rapidly terminate polymerization reaction and endows PVC resin with higher aging whiteness.
(2) The invention can keep the composite terminator uniform and stable without adding emulsifier, and avoids the influence of the emulsifier on the resin.
(3) The invention provides a vinyl chloride polymerization terminator with good low-temperature fluidity, which not only can play a good vinyl chloride polymerization terminating effect and improve the thermal stability of resin, but also has good low-temperature fluidity so as to be convenient for use in cold regions or seasons.
Detailed Description
The present invention will be further described with reference to the following examples.
Examples 1 to 5
The components and contents of the terminators for vinyl chloride polymerization having good low-temperature fluidity in examples 1 to 5 are shown in Table 1.
The material components were weighed according to the ratios in table 1. 20-30 g of diethylhydroxylamine, 30-40 g of ethylene glycol diglycidyl ether, 20-30 g of diphenyl isodecyl phosphite, 40-50 g of deionized water, 0.5-2 g of a polyvinyl alcohol aqueous solution with the polymerization degree of 350, the alcoholysis degree of 55% and the concentration of 5% are put into a glass beaker to be stirred for 10 minutes, and the mixture is added into a high-speed shearing emulsifying machine to be emulsified for 30 minutes at the rotating speed of 2000r/min, so that the vinyl chloride polymerization terminator with good low-temperature fluidity and uniform and stable existence of all components is obtained.
TABLE 1
The vinyl chloride polymerization terminator having good low-temperature fluidity prepared in examples 1 to 5 was used for terminating vinyl chloride polymerization.
The method is implemented according to the following processes and conditions: 2.3kg of desalted water, 9g of a 5% aqueous polyvinyl alcohol PVA80 solution, 6.4g of a 3% aqueous hydroxypropyl methylcellulose E50 solution, 0.265g of tert-butyl peroxyneodecanoate having a content of 75% and 0.530g of tert-amyl peroxypivalate having a content of 75% were placed in a 5L stainless steel autoclave equipped with two layers of bilobalt. Pumping the pressure in the kettle to be lower than-0.09 MPa, adding 1kg of vinyl chloride monomer, starting stirring, controlling the rotating speed to be 450rpm, firstly stirring and mixing for 10min at normal temperature, then raising the temperature of the kettle to be 58.0 ℃, and starting reaction timing after the temperature is stable. When the pressure in the autoclave had dropped by 0.34MPa, 0.5g of a terminator was charged into the autoclave. The temperature of the polymerization kettle is continuously controlled to be 58 +/-0.5 ℃, and the pressure drop in the polymerization kettle within 60min is observed and recorded to represent the terminating efficiency of the terminating agent (the smaller the pressure drop is, the higher the terminating efficiency of the terminating agent is, and the lower the terminating efficiency is, the reverse is). And recovering unreacted vinyl chloride monomer in the polymerization kettle, centrifugally dewatering the obtained slurry, and drying in a 60 ℃ circulating air drying oven for 6 hours to obtain PVC resin powder. And carrying out an aging whiteness test on the prepared PVC resin powder according to GB/T15595-2008.
Comparative examples 1 to 5:
the components of the materials are weighed according to the mixture ratio shown in the table 2, and the terminating agent is emulsified and compounded according to the process conditions of the embodiment 1-5.
TABLE 2 COMPARATIVE EXAMPLES 1 TO 5 (in parts by mass)
The methods and conditions for evaluating the terminators prepared in comparative examples 1 to 5 are the same as those of examples, i.e., the terminators prepared in comparative examples 1 to 5 are used for terminating the polymerization of vinyl chloride. The amount of the terminator added was also 1 g. The test method of the thermal stability of the PVC resin congo red is the same as that of the example.
The termination efficiency of the terminators obtained in examples and comparative examples, and the Congo red heat-stable time of the resin are shown in Table 3.
TABLE 3 termination efficiency of the terminator, Congo Red thermal stability time of the resin
It can be seen from the examples and comparative examples that the composite terminator composed of diethylhydroxylamine, ethylene glycol diglycidyl ether, and diphenyl isodecyl phosphite has good low-temperature fluidity, and has synergistic effect in terminating polymerization and improving the aging whiteness of resin, and can not only achieve good vinyl chloride polymerization terminating effect, but also effectively improve the aging whiteness of resin. The effects of synergistically terminating polymerization and improving the aged whiteness of the resin cannot be achieved by using one or two of diethylhydroxylamine, ethylene glycol diglycidyl ether and diphenyl-isodecyl phosphite.
Claims (10)
1. A vinyl chloride polymerization terminator having excellent low-temperature fluidity, characterized in that: the paint comprises the following components in parts by weight:
20-30 parts of diethylhydroxylamine; 30-40 parts of ethylene glycol diglycidyl ether; 20-30 parts of diphenyl isodecyl phosphite; 40-50 parts of deionized water and 0.5-2 parts of a dispersing agent.
2. A vinyl chloride polymerization terminator having good low-temperature fluidity according to claim 1, characterized in that: the dispersing agent is polyvinyl alcohol aqueous solution with polymerization degree of 300-400, alcoholysis degree of 50-60% and concentration of 3-6%.
3. A process for producing a vinyl chloride polymerization terminator having good low-temperature fluidity according to claim 1 or 2, characterized in that: the method comprises the following steps: all the components are put into a glass beaker to be mixed and stirred, and then are added into a high-speed shearing emulsifying machine to be emulsified, so that the vinyl chloride polymerization terminator with good low-temperature fluidity is obtained.
4. The method of producing a vinyl chloride polymerization terminator having good low-temperature fluidity according to claim 3, characterized in that: the mixing and stirring time is 10-20 min.
5. The method of producing a vinyl chloride polymerization terminator having good low-temperature fluidity according to claim 3, characterized in that: adding the mixture into a high-speed shearing emulsifying machine to emulsify for 20-30 min at the rotating speed of 1500-3000 r/min.
6. Use of a vinyl chloride polymerization terminator having good low-temperature fluidity according to claim 1 or 2, characterized in that: adding desalted water, a polyvinyl alcohol PVA80 aqueous solution, a hydroxypropyl methyl cellulose E50 aqueous solution, tert-butyl peroxyneodecanoate and tert-amyl peroxypivalate into a reaction kettle, pumping the pressure in the kettle to be lower than-0.09 MPa, adding a vinyl chloride monomer, starting stirring, stirring and mixing at normal temperature, heating, reacting, and adding the vinyl chloride polymerization terminator with good low-temperature fluidity into the kettle when the pressure in the kettle is reduced by 0.25-0.35 MPa.
7. Use according to claim 6, characterized in that: the reaction kettle is a 5L stainless steel pressure reaction kettle provided with two layers of double-blade flat slurry.
8. Use according to claim 6, characterized in that: and (3) adding vinyl chloride monomer, starting stirring, controlling the rotating speed at 440-470 rpm, stirring and mixing for 10-15 min at normal temperature, then heating to 58.0 +/-0.2 ℃, starting reaction timing after the temperature is stabilized, and filling the vinyl chloride polymerization terminator with good low-temperature fluidity into the kettle when the pressure in the kettle is reduced by 0.25-0.35 MPa.
9. Use according to claim 6, characterized in that: adding 1.8-2.4 kg of desalted water, 8-10 g of 5% polyvinyl alcohol PVA80 aqueous solution, 6.3-6.5 g of 3% hydroxypropyl methyl cellulose E50 aqueous solution, 0.255-0.267 g of 75% tert-butyl peroxyneodecanoate and 0.500-0.533 g of 75% tert-amyl peroxypivalate into a reaction kettle, pumping the pressure in the kettle to be lower than-0.09 MPa, adding 1kg of vinyl chloride monomer, starting stirring, controlling the rotating speed to be 440-470 rpm, firstly stirring and mixing for 10-15 min at normal temperature, then raising the temperature of the kettle to 58.0 +/-0.2 ℃, starting reaction timing after the temperature is stabilized, and filling the vinyl chloride polymerization terminator with good low-temperature fluidity into the kettle when the pressure in the kettle is reduced by 0.25-0.35 MPa.
10. Use according to claim 9, characterized in that: the addition amount of the vinyl chloride polymerization terminator with good low-temperature fluidity is 400-800 ppm based on the weight of vinyl chloride.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114044842A (en) * | 2021-11-23 | 2022-02-15 | 乌鲁木齐市华泰隆化学助剂有限公司 | Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof |
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CN102181000A (en) * | 2011-04-02 | 2011-09-14 | 西安道尔达化工有限公司 | Water-emulsion-type high-efficiency terminator for polyvinyl chloride and preparation method thereof |
CN102952225A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Suspension polymerization method for reducing polyvinyl chloride resin fisheyes |
CN108290979A (en) * | 2016-09-26 | 2018-07-17 | 株式会社Lg化学 | Chlorovinyl polymer composites and preparation method thereof and chlorovinyl polymer composite compositions |
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Patent Citations (4)
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US20040183054A1 (en) * | 2001-03-02 | 2004-09-23 | Dover Chemical Corporation | Phosphite ester additive compositions |
CN102181000A (en) * | 2011-04-02 | 2011-09-14 | 西安道尔达化工有限公司 | Water-emulsion-type high-efficiency terminator for polyvinyl chloride and preparation method thereof |
CN102952225A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Suspension polymerization method for reducing polyvinyl chloride resin fisheyes |
CN108290979A (en) * | 2016-09-26 | 2018-07-17 | 株式会社Lg化学 | Chlorovinyl polymer composites and preparation method thereof and chlorovinyl polymer composite compositions |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114044842A (en) * | 2021-11-23 | 2022-02-15 | 乌鲁木齐市华泰隆化学助剂有限公司 | Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof |
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