CN111333758A - Production method of environment-friendly polyvinyl chloride resin - Google Patents
Production method of environment-friendly polyvinyl chloride resin Download PDFInfo
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- CN111333758A CN111333758A CN202010260616.8A CN202010260616A CN111333758A CN 111333758 A CN111333758 A CN 111333758A CN 202010260616 A CN202010260616 A CN 202010260616A CN 111333758 A CN111333758 A CN 111333758A
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- polyvinyl chloride
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- chloride resin
- latex
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- 239000011347 resin Substances 0.000 title claims abstract description 54
- 229920005989 resin Polymers 0.000 title claims abstract description 54
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 40
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- 239000004816 latex Substances 0.000 claims abstract description 37
- 229920000126 latex Polymers 0.000 claims abstract description 37
- 238000001694 spray drying Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006172 buffering agent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 9
- -1 azo compound Chemical class 0.000 claims description 42
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/24—Treatment of polymer suspensions
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a production method of environment-friendly polyvinyl chloride resin, which is implemented by adopting a DCS distributed control system to control the following steps: a) adding 100 parts of vinyl chloride monomer, 60-90 parts of deionized water, 0.01-0.2 part of initiator and 1-4 parts of emulsifier into a dispersion tank according to mass parts, and homogenizing at normal temperature for 50-80 min; b) adding the homogenized mixture into a polymerization kettle, heating to 40-55 ℃, and carrying out polymerization reaction by adopting a micro-suspension polymerization process to obtain latex; c) after the polymerization reaction is finished, adding 0.01-2 parts of environment-friendly nonionic surfactant to adjust the viscosity of the latex; d) adding 0.01-0.1 part of buffering agent to adjust the pH value; e) and (3) carrying out spray drying on the latex to obtain the environment-friendly polyvinyl chloride resin. The polyvinyl chloride resin produced by the method meets the requirement of downstream manufacturers on the environmental protection of the resin through SVHC (REACH high attention substance detection), heavy metal and polycyclic aromatic hydrocarbon detection.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a production method of environment-friendly polyvinyl chloride resin.
Background
The special PVC resin is an important raw material in the chemical industry, and is mainly used for producing wall paper, artificial leather, floor leather, flame-retardant conveyor belts, toys and other products. With the improvement of environmental protection requirements of processed products such as toys and the like, particularly export products, part of downstream manufacturers propose to carry out environment-friendly SVHC (real high attention substance detection), six heavy metal detection and polycyclic aromatic hydrocarbon detection on resin products. Because the existing auxiliary agent for producing the special resin contains components which are limited by environmental protection laws and regulations, PVC products such as toys, gloves and the like produced by downstream customers by using the special resin have partial standard exceeding conditions. Therefore, the development of environment-friendly special resin has important significance.
Disclosure of Invention
In order to solve the problems, the invention provides a method for producing environment-friendly polyvinyl chloride resin, which aims to produce environment-friendly polyvinyl chloride resin meeting the environment-friendly standard.
The invention adopts the following technical scheme:
a production method of various environment-friendly polyvinyl chloride resins is implemented by adopting a DCS distributed control system to control the following steps:
a) adding 100 parts of vinyl chloride monomer, 60-90 parts of deionized water, 0.01-0.2 part of initiator and 1-4 parts of emulsifier into a dispersion tank according to mass parts, and homogenizing at normal temperature for 50-80 min;
b) adding the homogenized mixture into a polymerization kettle, heating to 40-55 ℃, and carrying out polymerization reaction for 10-20 hours by adopting a micro suspension polymerization process to obtain latex with the particle size of 0.1-2 mu m;
c) after the polymerization reaction is finished, adding 0.01-2 parts of environment-friendly nonionic surfactant to adjust the viscosity of the latex;
d) adding 0.01-0.1 part of buffering agent to adjust the pH value;
e) carrying out spray drying on the latex to obtain environment-friendly polyvinyl chloride resin;
or, the DCS distributed control system is adopted to carry out the following steps:
a) adding 100 parts of vinyl chloride monomer, 60-90 parts of deionized water, 0.01-0.2 part of initiator and 1-4 parts of emulsifier into a dispersion tank according to mass parts, and homogenizing at normal temperature for 50-80 min;
b) adding the homogenized mixture into a polymerization kettle, and adding 0.01-0.1 part of buffering agent to adjust the pH value;
c) heating the polymerization kettle to 40-55 ℃, and carrying out polymerization reaction for 10-20 h by adopting a micro suspension polymerization process to obtain latex with the particle size of 0.1-2 mu m;
d) after the polymerization reaction is finished, adding 0.01-2 parts of environment-friendly nonionic surfactant to adjust the viscosity of the latex;
e) adding 0.01-0.1 part of buffering agent to adjust the pH value;
f) carrying out spray drying on the latex to obtain environment-friendly polyvinyl chloride resin;
or, the DCS distributed control system is adopted to carry out the following steps:
a) adding 100 parts of vinyl chloride monomer, 60-90 parts of deionized water, 0.01-0.2 part of initiator and 1-4 parts of emulsifier into a dispersion tank according to mass parts, and homogenizing at normal temperature for 50-80 min;
b) adding the homogenized mixture into a polymerization kettle, and adding 0.01-0.1 part of buffering agent to adjust the pH value;
c) heating the polymerization kettle to 40-55 ℃, and carrying out polymerization reaction for 10-20 h by adopting a micro suspension polymerization process to obtain latex with the particle size of 0.1-2 mu m;
d) after the polymerization reaction is finished, adding 0.01-2 parts of environment-friendly nonionic surfactant to adjust the viscosity of the latex;
e) and (3) carrying out spray drying on the latex to obtain the environment-friendly polyvinyl chloride resin.
Compared with the prior art, the invention has the advantages that: by using the buffering agent, the pH values of the reaction system and the latex after reaction can be adjusted in time; by using the environment-friendly nonionic surfactant, the produced special resin meets the requirement of downstream manufacturers on the environmental protection of the resin through SVHC (real high attention substance detection), heavy metal and polycyclic aromatic hydrocarbon detection.
Further, spray drying is carried out by adopting a spray drying system, wherein the inlet temperature of the spray drying system is controlled to be 120-160 ℃, and the outlet temperature of the spray drying system is controlled to be 50-80 ℃.
Further, the initiator is an azo compound, an organic peroxide or a mixture of the azo compound and the organic peroxide compounded according to the mass ratio of 0.5-3.
Further, the azo compound is one or more of oil-soluble azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobisisobutyronitrile formamide, azobisdicyclohexyl-methyl cyanide, dimethyl azobisisobutyrate, water-soluble azobisisobutyramidine hydrochloride, azobisisopropylimidazoline and azobiscyanovaleric acid.
Further, the organic peroxide initiator is one or more of ethyl ethoxypropionate, p-3, 5-trimethyl-n-hexanoyl peroxide and di (2-ethylhexyl) peroxydicarbonate.
Further, the emulsifier is prepared from an anionic surfactant and a nonionic surfactant in a mass ratio of 1: 0-1.8; during preparation, water is heated to a temperature higher than the melting point of the nonionic surfactant, then the nonionic surfactant is added, after stirring for 5-30 min, the anionic surfactant is added, and stirring is continued for 30-120 min for later use.
Further, the anionic surfactant is one or more of alkyl (C11-C18) fatty acid salt, alkyl (C10-C18) sulfate, alkyl (C12-C16) benzene sulfonate, alkyl aryl sulfonate, alkyl succinic acid sulfonate and polyoxyethylene ether sulfate.
Further, the nonionic surfactant is one or more of long-chain alkyl fatty alcohol, epoxy alkyl fatty alcohol, polyoxyethylene alkyl ester, polyoxyethylene alkyl ether, sorbitan fatty acid ester and sorbitan fatty acid ester.
Further, the environment-friendly nonionic surfactant is one or more of castor oil polyoxyethylene ester, polyoxyethylene fatty acid ester, polyoxyethylene ester fatty alcohol ether and polyoxyethylene alkyl alcohol amine.
Further, the buffer is one or more of sodium bicarbonate, sodium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium bicarbonate or organic amine.
Detailed Description
The invention will be described below by means of specific examples. It should be understood by those skilled in the art that the examples are only for illustrating the present invention and not for limiting the present invention.
According to one aspect of the present invention, there is provided a method for producing an environment-friendly polyvinyl chloride resin, the specific examples are as follows:
example 1
Adding water into a container, heating the water to 65 deg.C (higher alcohol melting point of 47-53 deg.C), adding 35.98g long chain alkyl fatty alcohol, stirring for 5min, adding 26.23g sodium dodecyl benzene sulfonate, and stirring for 30min to obtain emulsifier. 3600g of vinyl chloride monomer, 3200g of deionized water, 5.0g of azobisisobutyronitrile, 2.2g of ethyl ethoxypropionate and the prepared emulsifier were added to a dispersion tank, and homogenized at normal temperature for 50 min. Adding the homogenized mixture into a polymerization kettle, heating to 40 ℃, and carrying out polymerization reaction for 10 hours by adopting a micro suspension polymerization process to obtain latex with the particle size of 0.1-2 mu m. After the polymerization was completed, 1.52g of castor oil polyoxyethylene ester was added to the polymerization vessel to adjust the viscosity of the latex, and 0.36g of ammonium bicarbonate was added to the polymerization vessel to adjust the pH of the latex. Spray drying the adjusted latex using a spray drying system to obtain a polyvinyl chloride resin, wherein the inlet temperature of the spray drying system is controlled at 120 ℃ and the outlet temperature is controlled at 50 ℃. The polyvinyl chloride resin obtained in the embodiment is subjected to environment-friendly detection, and the SVHC test result is less than or equal to 0.1% (w/w), and meets the European Union detection standard. And (3) feeding the obtained environment-friendly polyvinyl chloride resin into a grinder for further grinding, and storing the resin finished product environment-friendly resin with the particle size of 2-5 mu m into a storage bin. Tables 1 and 2 show the results of the SVHC test for different substances, respectively.
TABLE 1 test results for substances of high interest in SVHC candidate lists
Table 2 test results for additional identified SVHC
Example 2
Adding water into a container, heating the water to a temperature higher than 65 ℃, adding 36.63g of epoxy alkyl fatty alcohol, stirring for 15min, adding 26.78g of sodium dodecyl benzene sulfonate, and stirring for 80min to obtain the emulsifier for later use. 3700g of vinyl chloride monomer, 3320g of deionized water, 5.2g of azobisisobutyronitrile, 2.1g of p-3.5.5-trimethyl-n-hexanoyl peroxide and the prepared emulsifier were added to a dispersion tank and homogenized at normal temperature for 70 min. The homogenized mixture was added to a polymerization kettle, to which was added 0.36g of ammonium bicarbonate. Heating the polymerization kettle to 50 ℃, and carrying out polymerization reaction for 15 hours by adopting a micro suspension polymerization process to obtain the latex with the particle size of 0.1-2 mu m. After the polymerization reaction was completed, 1.55g of polyoxyethylene fatty acid ester was added to the polymerization vessel to adjust the viscosity of the latex, and 0.5g of ammonium hydrogencarbonate was further added to the polymerization vessel to adjust the pH of the latex. Spray drying the adjusted latex using a spray drying system to obtain a polyvinyl chloride resin, wherein the inlet temperature of the spray drying system is controlled at 140 ℃ and the outlet temperature is controlled at 65 ℃. The polyvinyl chloride resin obtained in the embodiment is subjected to environment-friendly detection, and the SVHC test result is less than or equal to 0.1% (w/w), and meets the European Union detection standard. And (3) feeding the obtained environment-friendly polyvinyl chloride resin into a grinder for further grinding, and storing the resin finished product environment-friendly resin with the particle size of 2-5 mu m into a storage bin. Tables 3 and 4 show the results of the SVHC test for different substances, respectively.
TABLE 3 test results for substances of high interest in the SVHC candidate list
TABLE 4 test results for additional identified SVHC
Example 3
Adding water into a container, heating the water to a temperature higher than 65 ℃, adding 35.98g of epoxy alkyl fatty alcohol, stirring for 30min, adding 26.23g of sodium dodecyl benzene sulfonate, and stirring for 120min to obtain the emulsifier for later use. 3600g of vinyl chloride monomer, 3230g of deionized water, 5.2g of azobisisovaleronitrile, 2.0g of di (2-ethylhexyl) oxydicarbonate and the prepared emulsifier were added to a dispersion tank and homogenized at room temperature for 80 min. The homogenized mixture was charged into a polymerization vessel, to which was further added 0.39g of sodium bicarbonate. Heating the polymerization kettle to 55 ℃, and carrying out polymerization reaction for 20 hours by adopting a micro suspension polymerization process to obtain the latex with the particle size of 0.1-2 mu m. After completion of the polymerization, 1.52g of polyoxyethylene fatty acid ester was added to the polymerization vessel to adjust the viscosity of the latex. Spray drying the adjusted latex using a spray drying system to obtain a polyvinyl chloride resin, wherein the inlet temperature of the spray drying system is controlled at 160 ℃ and the outlet temperature is controlled at 80 ℃. The polyvinyl chloride resin obtained in the embodiment is subjected to environment-friendly detection, and the SVHC test result is less than or equal to 0.1% (w/w), and meets the European Union detection standard. And (3) feeding the obtained environment-friendly polyvinyl chloride resin into a grinder for further grinding, and storing the resin finished product environment-friendly resin with the particle size of 2-5 mu m into a storage bin. Tables 5 and 6 show the results of the SVHC test for different substances, respectively.
TABLE 5 test results for substances of high interest in the SVHC candidate list
TABLE 6 test results for additional identified SVHC
Comparative example
Adding water into a container, heating the water to above 65 deg.C, adding 34.65g long-chain alkyl fatty alcohol, stirring for 30min, adding 25.57g sodium dodecyl benzene sulfonate, and stirring for 90min to obtain the emulsifier. 3400g of vinyl chloride monomer, 3050g of deionized water, 4.9g of azobisisovaleronitrile and 1.8g of p-3.5.5-trimethyl-n-hexanoyl peroxide are added into a dispersion tank, and homogenized for 60min at normal temperature. The homogenized mixture was charged to a polymerization kettle, to which was added 0.34g of ammonium bicarbonate. Heating the polymerization kettle to 50 ℃, and carrying out polymerization reaction for 15 hours by adopting a micro suspension polymerization process to obtain the latex with the particle size of 0.1-2 mu m. After the polymerization reaction, 1.43g of non-environment-friendly nonionic surfactant nonylphenol polyoxyethylene ether was added to the polymerization kettle to adjust the viscosity of the latex. The adjusted latex was spray-dried using a spray-drying system to obtain a polyvinyl chloride resin. The polyvinyl chloride resin obtained in the embodiment is subjected to environment protection detection, and the SVHC test result is greater than 0.1% (w/w), and does not reach the European Union detection standard. Table 7 shows the test results for high interest substances in the SVHC candidate list.
TABLE 7 test results for substances of high interest in the SVHC candidate list
As is apparent from the comparison between the above examples and comparative examples, when the viscosity of the latex is adjusted using a non-eco-friendly nonionic surfactant as a viscosity modifier, the obtained polyvinyl chloride resin does not meet the environmental protection. The order of addition of the buffering agents does not affect the environmental protection of the obtained product, but affects the pH value of the polymerization system and improves the thermal stability of the resin.
In the steps of the above examples and comparative examples, a DCS distributed control system is used to fully automatically control the production processes of raw material configuration, homogenization, polymerization, drying, etc., and parameters such as reaction conditions, etc., thereby completing the production of resin.
The above description is only a preferred embodiment of the present invention, and those skilled in the art will appreciate that any modification, variation and substitution made without departing from the spirit and scope of the present invention are within the protection scope of the present invention.
Claims (10)
1. The production method of the environment-friendly polyvinyl chloride resin is characterized by being implemented by adopting a DCS distributed control system to control the following steps:
a) adding 100 parts of vinyl chloride monomer, 60-90 parts of deionized water, 0.01-0.2 part of initiator and 1-4 parts of emulsifier into a dispersion tank according to mass parts, and homogenizing at normal temperature for 50-80 min;
b) adding the homogenized mixture into a polymerization kettle, heating to 40-55 ℃, and carrying out polymerization reaction for 10-20 hours by adopting a micro suspension polymerization process to obtain latex with the particle size of 0.1-2 mu m;
c) after the polymerization reaction is finished, adding 0.01-2 parts of environment-friendly nonionic surfactant to adjust the viscosity of the latex;
d) adding 0.01-0.1 part of buffering agent to adjust the pH value;
e) carrying out spray drying on the latex to obtain environment-friendly polyvinyl chloride resin;
or, the DCS distributed control system is adopted to control the following steps to implement:
adding 100 parts of vinyl chloride monomer, 60-90 parts of deionized water, 0.01-0.2 part of initiator and 1-4 parts of emulsifier into a dispersion tank according to mass parts, and homogenizing at normal temperature for 50-80 min;
adding the homogenized mixture into a polymerization kettle, and adding 0.01-0.1 part of buffering agent to adjust the pH value;
c) heating the polymerization kettle to 40-55 ℃, and carrying out polymerization reaction for 10-20 h by adopting a micro suspension polymerization process to obtain latex with the particle size of 0.1-2 mu m;
d) after the polymerization reaction is finished, adding 0.01-2 parts of environment-friendly nonionic surfactant to adjust the viscosity of the latex;
e) adding 0.01-0.1 part of buffering agent to adjust the pH value;
f) carrying out spray drying on the latex to obtain environment-friendly polyvinyl chloride resin;
or, the DCS distributed control system is adopted to control the following steps to implement:
a) adding 100 parts of vinyl chloride monomer, 60-90 parts of deionized water, 0.01-0.2 part of initiator and 1-4 parts of emulsifier into a dispersion tank according to mass parts, and homogenizing at normal temperature for 50-80 min;
b) adding the homogenized mixture into a polymerization kettle, and adding 0.01-0.1 part of buffering agent to adjust the pH value;
c) heating the polymerization kettle to 40-55 ℃, and carrying out polymerization reaction for 10-20 h by adopting a micro suspension polymerization process to obtain latex with the particle size of 0.1-2 mu m;
d) after the polymerization reaction is finished, adding 0.01-2 parts of environment-friendly nonionic surfactant to adjust the viscosity of the latex;
e) and (3) carrying out spray drying on the latex to obtain the environment-friendly polyvinyl chloride resin.
2. The method for producing environment-friendly polyvinyl chloride resin according to claim 1, wherein the spray drying is performed by a spray drying system, an inlet temperature of the spray drying system is controlled to be 120-160 ℃, and an outlet temperature of the spray drying system is controlled to be 50-80 ℃.
3. The method for producing environment-friendly polyvinyl chloride resin according to claim 1, wherein the initiator is an azo compound, an organic peroxide or a mixture of the azo compound and the organic peroxide compounded according to a mass ratio of 0.5 to 3.
4. The method for producing environmentally friendly polyvinyl chloride resin according to claim 3, wherein said azo compound is one or more of oil-soluble azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobisisobutyronitrile formamide, azobisdicyclohexyl-methane, dimethyl azobisisobutyrate, and water-soluble azobisisobutyramidine hydrochloride, azobisisopropylimidazoline, and azobiscyanovaleric acid.
5. The method for producing environmentally friendly polyvinyl chloride resin according to claim 3, wherein the organic peroxide initiator is one or more of ethyl ethoxypropionate, p-3, 5-trimethyl-n-hexanoyl peroxide, di (2-ethylhexyl) peroxydicarbonate.
6. The method for producing the environment-friendly polyvinyl chloride resin as claimed in claim 1, wherein the emulsifier is prepared from an anionic surfactant and a nonionic surfactant in a mass ratio of 1: 0-1.8; during preparation, water is heated to a temperature higher than the melting point of the nonionic surfactant, then the nonionic surfactant is added, after stirring for 5-30 min, the anionic surfactant is added, and stirring is continued for 30-120 min for later use.
7. The method for producing environmentally friendly polyvinyl chloride resin as claimed in claim 6, wherein the anionic surfactant is one or more selected from alkyl (C11-C18) fatty acid salt, alkyl (C10-C18) sulfate, alkyl (C12-C16) benzene sulfonate, alkyl aryl sulfonate, alkyl succinic acid sulfonate, and polyoxyethylene ether sulfate.
8. The method for producing environment-friendly polyvinyl chloride resin according to claim 6, wherein the nonionic surfactant is one or more of long-chain alkyl fatty alcohol, epoxy alkyl fatty alcohol, polyoxyethylene alkyl ester, polyoxyethylene alkyl ether, sorbitan fatty acid ester, and sorbitan fatty acid ester.
9. The method for producing environmentally friendly polyvinyl chloride resin according to claim 1, wherein the environmentally friendly nonionic surfactant is one or more of castor oil polyoxyethylene ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene alkyl alcohol amine.
10. The method for producing environmentally friendly polyvinyl chloride resin according to claim 1, wherein the buffer is one or more of sodium bicarbonate, sodium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium bicarbonate or organic amine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114299038A (en) * | 2021-12-31 | 2022-04-08 | 英科医疗科技股份有限公司 | A DCS control system for PVC glove production |
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