CN114478893B - Hydrophilic vinyl chloride copolymer resin and preparation method thereof - Google Patents
Hydrophilic vinyl chloride copolymer resin and preparation method thereof Download PDFInfo
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- CN114478893B CN114478893B CN202111641768.3A CN202111641768A CN114478893B CN 114478893 B CN114478893 B CN 114478893B CN 202111641768 A CN202111641768 A CN 202111641768A CN 114478893 B CN114478893 B CN 114478893B
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- glycidyl methacrylate
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229920006026 co-polymeric resin Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 18
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 239000003999 initiator Substances 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000006172 buffering agent Substances 0.000 claims description 9
- 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 8
- 238000006136 alcoholysis reaction Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 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 6
- 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-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
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 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 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920003086 cellulose ether Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010558 suspension polymerization method Methods 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 13
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 239000000872 buffer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- -1 hydroxymethyl propyl Chemical group 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
- C08F214/00—Copolymers 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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a hydrophilic vinyl chloride copolymer resin and a preparation method thereof. According to the invention, a suspension polymerization method is adopted, and hydrophilic groups are introduced into PVC skeleton molecules through free radical copolymerization of glycidyl methacrylate and vinyl chloride, so that the hydrophilicity of the product is improved. Since glycidyl methacrylate contains a soft segment, copolymerization with vinyl chloride can exert an effect of internal plasticization. The preparation method is simple to operate, the auxiliary agent residue in the prepared product is less, the product purity is high, and the transparency is good. The hydrophilic vinyl chloride copolymer resin provided has good hydrophilic performance and mechanical property, and has wide application value in the fields of biomedicine, separation membrane materials, articles for daily use and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a hydrophilic vinyl chloride copolymer resin and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is widely used in various fields of life due to its excellent comprehensive mechanical properties, flame retardancy, chemical stability, low price, etc. However, polyvinyl chloride resin has the defects of poor hydrophilicity, poor impact resistance and the like due to the characteristics of the molecular structure, and the application of the polyvinyl chloride resin in many aspects is limited. In order to improve the performance deficiency of PVC, a great deal of PVC modification research is carried out, and various methods for modifying PVC physically and chemically are formed. Therefore, the development of a novel vinyl chloride copolymer resin has become one of the most active research fields in polymer science.
Because the PVC is hydrophobic, hydrophilic components are introduced to form amphiphilic polymers, the mechanical property and the functionality of the material can be provided at the same time, and the structure and the function of the functional polymers can be effectively unified. At present, the hydrophilic PVC is prepared at home and abroad mainly by an atom transfer radical grafting method, a surface coating method, a blending method and the like. The atom transfer radical polymerization grafting method has the advantages of complex operation process, low yield, long time consumption and unfavorable application and popularization; the surface coating method is an efficient and simple method, but a hydrophilic layer coated on the surface is unstable and is easy to wash away by water; blending with hydrophilic polymers is a simple process suitable for large-scale production, but often organic additives are not compatible with PVC. At present, how to improve the hydrophilic performance of PVC and improve the mechanical performance is still an urgent problem to be solved.
Disclosure of Invention
The invention aims to provide a hydrophilic vinyl chloride copolymer resin and a preparation method thereof, and the provided hydrophilic vinyl chloride copolymer resin has good hydrophilic property and mechanical property and has wide application value in the fields of biomedicine, separation membrane materials, articles for daily use and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in one embodiment, the present invention provides a hydrophilic vinyl chloride copolymer resin. The hydrophilic vinyl chloride copolymer resin comprises the following components in parts by mass:
50-100 parts of chloroethylene;
1-30 parts of glycidyl methacrylate;
0.05 to 1.2 portions of initiator;
0.02-0.2 part of dispersing agent;
0.01 to 0.3 part of buffer;
100-500 parts of deionized water.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 65-95 parts by weight of vinyl chloride.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 5-25 parts by weight of glycidyl methacrylate.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 0.08-1 part of initiator in parts by weight. Preferably, the initiator comprises azo initiator and organic peroxide initiator;
further preferably, the initiator comprises one or more of azobisisobutyronitrile, azobisisovaleronitrile, di (2-ethylhexyl) peroxydicarbonate, and cumyl peroxyneodecanoate.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 0.05-0.18 part of dispersing agent in parts by weight.
Preferably, the dispersant includes one or more of a hydrophilic organic polymer compound and a water-insoluble inorganic solid powder.
Further preferably, the dispersing agent is one or more of gelatin, cellulose ethers, partially alcoholyzed polyvinyl alcohol, styrene-maleic anhydride copolymer, magnesium hydroxide, basic calcium phosphate and calcium carbonate. The alcoholysis degree of the partial alcoholysis is 40-85%.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 0.03-0.2 parts of buffering agent in parts by weight. Preferably, the buffering agent is a buffering agent known in the art, such as ammonium bicarbonate, sodium bicarbonate, and the like. These buffers may be used alone or in combination of two or more.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 200-400 parts of deionized water in parts by weight.
Preferably, the glycidyl methacrylate is an emulsified glycidyl methacrylate. It comprises, in parts by mass, per 1 part of emulsified glycidyl methacrylate: 1 part of glycidyl methacrylate, 0.005-0.01 part of emulsifier and 3-20 parts of deionized water. The emulsifier is sodium dodecyl benzene sulfonate.
The order of adding the glycidyl methacrylate into the polymerizer is not limited, and includes one of a one-time addition, a stepwise addition, and a continuous addition. The polymerization vessel may be charged with the auxiliary before the reaction or at any time period of the reaction, preferably at the middle and late stages of the polymerization reaction, more preferably at the middle and early stages of the reaction.
In a specific embodiment, the invention also provides a preparation method of the hydrophilic vinyl chloride copolymer resin, which comprises the following steps:
(1) Sealing the polymerization kettle, replacing with nitrogen, and vacuumizing to-0.1 MPa;
(2) Adding deionized water, a dispersing agent, an initiator, vinyl chloride, glycidyl methacrylate and a buffering agent into a polymerization kettle for free radical copolymerization reaction;
(3) When the pressure in the reaction kettle is reduced to 0.1-0.3 MPa, the reaction kettle is cooled to stop the reaction, the stirring rotation speed is reduced, the bottom valve is opened for discharging, and the hydrophilic vinyl chloride copolymer resin is obtained after deionized water is cleaned, centrifuged and dried.
Further, the temperature of the copolymerization reaction in the step (2) is 10-90 ℃, and the rotating speed of the copolymerization reaction is 300-3000 rmp.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a suspension polymerization method is adopted, and hydrophilic groups are introduced into PVC skeleton molecules through free radical copolymerization of glycidyl methacrylate and vinyl chloride, so that the hydrophilicity of the product is improved. Since glycidyl methacrylate contains a soft segment, copolymerization with vinyl chloride can exert an effect of internal plasticization. The preparation method is simple to operate, the auxiliary agent residue in the prepared product is less, the product purity is high, and the transparency is good. Not only stabilizing the performance of the copolymer, but also being suitable for mass production.
Detailed Description
The invention will be further illustrated below, these examples being given solely for the purpose of illustration and not for the purpose of limiting the scope of the invention; the experimental methods in the examples, for which specific conditions were not noted, were all according to conventional conditions; the reagents and materials used, unless otherwise indicated, are all those commercially available.
The invention provides a hydrophilic vinyl chloride copolymer resin, which comprises the following components in parts by mass:
50-100 parts of chloroethylene;
1-30 parts of glycidyl methacrylate;
0.05 to 1.2 portions of initiator;
0.02-0.2 part of dispersing agent;
0.01 to 0.3 part of buffer;
100-500 parts of deionized water;
the hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 65-95 parts by weight of vinyl chloride, more preferably 70-90 parts by weight.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 1 to 30 parts by weight of glycidyl methacrylate, preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 0.08-1 part of initiator, more preferably 0.1-0.8 part of initiator. The mass concentration of the initiator is preferably 40% -80%, more preferably 50% -60%. The initiator in the present invention is preferably a relatively high activity initiator, more preferably a mixture of a relatively high activity initiator and a medium activity initiator.
Preferably, the initiator comprises one or more of azobisisobutyronitrile, azobisisovaleronitrile, di (2-ethylhexyl) peroxydicarbonate and cumyl peroxyneodecanoate.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 0.05 to 0.18 part by weight of a dispersing agent, more preferably 0.07 to 0.15 part by weight. In a specific embodiment, the dispersing agent is a compound use of a dispersing agent A, a dispersing agent B, a dispersing agent C and a dispersing agent D. The dispersing agent A is polyvinyl alcohol with the alcoholysis degree of 65-75%, the dispersing agent B is polyvinyl alcohol with the alcoholysis degree of 75-85%, the dispersing agent C is hydroxymethyl propyl cellulose, and the dispersing agent D is polyvinyl alcohol with the alcoholysis degree of 40-60%.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 0.03 to 0.2 part by weight of a buffer agent, more preferably 0.05 to 0.15 part by weight.
The hydrophilic vinyl chloride copolymer resin provided by the invention preferably contains 200-400 parts by weight of deionized water, more preferably 250-350 parts by weight.
The emulsified glycidyl methacrylate has higher activity and can better perform copolymerization reaction with vinyl chloride. In order to be able to add it uniformly to the polymerization vessel during the addition. Preferably, the glycidyl methacrylate is an emulsified glycidyl methacrylate. It comprises, in parts by mass, per 1 part of emulsified glycidyl methacrylate: 1 part of glycidyl methacrylate, 0.005-0.01 part of emulsifier and 3-20 parts of deionized water. The emulsifier is sodium dodecyl benzene sulfonate. The glycidyl methacrylate may be added to the polymerization vessel in such a manner that it is added at once before the reaction, preferably in stages, more preferably continuously. The polymerization vessel may be charged with the auxiliary before the reaction, preferably at the middle and late stages of the polymerization, and more preferably at the middle and early stages of the reaction.
The invention also provides a preparation method of the hydrophilic vinyl chloride copolymer resin, which comprises the following steps:
(1) Sealing the polymerization kettle, replacing with nitrogen, and vacuumizing to-0.1 MPa;
(2) Adding deionized water, a dispersing agent, an initiator, vinyl chloride, glycidyl methacrylate and a buffering agent into a polymerization kettle for free radical copolymerization reaction;
(3) When the pressure in the reaction kettle is reduced to 0.1-0.3 MPa, the reaction kettle is cooled to stop the reaction, the stirring rotation speed is reduced, the bottom valve is opened for discharging, and the hydrophilic vinyl chloride copolymer resin is obtained after deionized water is cleaned, centrifuged and dried.
Further, the temperature of the copolymerization reaction in the step (2) is 10 to 90 ℃, preferably 30 to 80 ℃, more preferably 40 to 70 ℃.
The rotational speed of the copolymerization reaction is 300 to 3000rmp, preferably 400 to 2000rmp, more preferably 600 to 1500rmp.
In order to further illustrate the present invention, the hydrophilic vinylchloride copolymer resin provided by the present invention is described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
After the polymerization vessel was sealed, nitrogen was used for three times, and then vacuum was applied to-0.1 MPa. 300 parts of deionized water, 0.1 part of dispersing agent (A: B: C: D=2:1:1:2), 0.07 part of initiator (cumyl peroxyneodecanoate: di (2-ethylhexyl peroxydicarbonate) =1.3:1), 97 parts of vinyl chloride, 3 parts of glycidyl methacrylate and 0.1 part of buffer (ammonium bicarbonate) are added into a polymerization kettle. Turning on a stirrer, turning on a rotating speed to 1000rmp, stirring for 30 minutes, turning on an oil bath switch, heating to 57.5 ℃, starting timing reaction, cooling the reaction kettle to stop reaction when the pressure in the reaction kettle is reduced to 0.2MPa, reducing the stirring rotating speed, opening a bottom valve for discharging, and sequentially cleaning with deionized water, centrifuging and drying to obtain the hydrophilic vinyl chloride copolymer resin.
Example 2
The initiator was replaced with 0.14 parts, and the same starting materials and preparation methods as in example 1 were used.
Example 3
Unlike example 2, 3 parts of glycidyl methacrylate were not added before the reaction, but after emulsification (3 parts of glycidyl methacrylate, 0.003 part of emulsifier (sodium dodecylbenzenesulfonate), 10 parts of deionized water) were added at once within 10 minutes after the temperature was raised to 57.5 for 20 minutes. The deionized water added before the reaction was changed to 270 parts, and the same raw materials and preparation methods as in example 2 were used.
Example 4
Unlike example 3, the emulsified glycidyl methacrylate was continuously added at a constant rate for 2 hours after the reaction was started for 20 minutes at a temperature of 57.5. The same starting materials and preparation methods as in example 3 were used.
Example 5
Unlike example 4, the emulsified glycidyl methacrylate was continuously added in 6 parts (composition comprising 6 parts of glycidyl methacrylate, 0.006 parts of emulsifier, 10 parts of deionized water), and the deionized water added before the reaction was changed to 240 parts. The same starting materials and preparation methods as in example 2 were used.
Example 6
Unlike example 4, 9 parts of emulsified glycidyl methacrylate (composition comprising 9 parts of glycidyl methacrylate, 0.01 part of emulsifier, 5 parts of deionized water) was continuously added, and the deionized water added before the reaction was changed to 250 parts. The same starting materials and preparation methods as in example 2 were used.
Comparative example 1
Unlike example 1, no glycidyl methacrylate was added, the initiator was changed to 0.07 parts, and deionized water was changed to 300 parts. Other materials and preparation methods same as those of example 1 were used to prepare a general polyvinyl chloride resin.
Test case
100 parts of the vinyl chloride copolymer resin and the vinyl chloride resin prepared in examples 1 to 6 and comparative example, 2 parts of a calcium zinc stabilizer and 0.6 part of stearic acid are mixed by a two-roll mill, then pressed into sample pieces by a plate pressing machine at 175 ℃, and the obtained sample pieces are cut and pressed by a fixed template to obtain dumbbell-shaped sample pieces and water contact angle sample pieces for measuring tensile properties. And respectively performing performance tests on the test pieces. Apparent density was tested with reference to the specification of GB/T20022-2005, water contact angle was tested with reference to the specification of GB/T30693-2014, and tensile properties were tested with reference to the specification of GB/T1040.2-2006.
TABLE 1 characterization of the properties of examples 1-6, comparative example 1
As can be seen from Table 1, the water contact angle of the copolymer resin of examples 1 to 6 was significantly reduced by 21% to 35% as the amount of glycidyl methacrylate added was increased as compared with comparative example 1.
The glycidyl methacrylate can delay the reaction after being added, and the reaction time is obviously prolonged. Increasing the amount of initiator can shorten the reaction time of the copolymerization of vinyl chloride and glycidyl methacrylate. The addition of the emulsified glycidyl methacrylate during the reaction can shorten the copolymerization reaction time. And the continuous addition of the emulsified glycidyl methacrylate further obviously shortens the copolymerization reaction time. In addition, as the content of glycidyl methacrylate added was increased, the water contact angle was reduced by 3.7% and 11.07%, respectively. This demonstrates that as the glycidyl methacrylate content increases, the water contact angle of the copolymer resin also decreases.
As can be seen from Table 1, examples 1 to 6 showed an improvement in tensile strength of 27.10% to 37.78% in terms of tensile strength with respect to the resin prepared in the comparative example, as the amount of glycidyl methacrylate was increased, as compared with comparative example 1. The apparent density is also significantly higher than that of the comparative resin. The elongation at break is obviously improved, which indicates that the mechanical property of the polyvinyl chloride can be improved by adding glycidyl methacrylate. As the amount of the emulsified glycidyl methacrylate added was increased, the water contact angle of the copolymer resin of examples was significantly reduced.
From the comparison of examples 1 to 6 and comparative example 1 above, it can be seen that the hydrophilic vinyl chloride copolymer resin provided by the present invention has good hydrophilicity and mechanical properties.
Example 7
After the polymerization vessel was sealed, nitrogen was used for displacement, and then vacuum was applied to-0.1 MPa. 100 parts of deionized water, 0.1 part of gelatin, 0.07 part of azobisisobutyronitrile, 97 parts of vinyl chloride, 3 parts of emulsified glycidyl methacrylate (composition comprising 3 parts of glycidyl methacrylate, 0.024 part of emulsifier, 30 parts of deionized water), and 0.01 part of buffer (sodium bicarbonate) were added to a polymerization vessel. Turning on a stirrer, turning on a rotating speed to 3000rmp, stirring for 20 minutes, turning on an oil bath switch, heating to 90 ℃, starting timing reaction, cooling the reaction kettle to stop reaction when the pressure in the reaction kettle is reduced to 0.2MPa, reducing the stirring rotating speed, opening a bottom valve for discharging, and sequentially cleaning with deionized water, centrifuging and drying to obtain the hydrophilic vinyl chloride copolymer resin.
Example 8
After the polymerization vessel was sealed, nitrogen was used for displacement, and then vacuum was applied to-0.1 MPa, and 300 parts of deionized water, 0.1 part of magnesium hydroxide, 0.07 part of azobisisovaleronitrile, 97 parts of vinyl chloride, 20 parts of emulsified glycidyl methacrylate (composition comprising 20 parts of glycidyl methacrylate, 0.2 part of emulsifier, 60 parts of deionized water), and 0.1 part of buffer (ammonium bicarbonate: sodium bicarbonate=2:1) were added to the polymerization vessel. Turning on a stirrer, turning on a rotating speed to 1500rmp, stirring for 25 minutes, turning on an oil bath switch, heating to 40 ℃, starting timing reaction, cooling the reaction kettle to stop reaction when the pressure in the reaction kettle is reduced to 0.2MPa, reducing the stirring rotating speed, opening a bottom valve for discharging, and sequentially cleaning with deionized water, centrifuging and drying to obtain the hydrophilic vinyl chloride copolymer resin.
Example 9
After the polymerization vessel was sealed, nitrogen was used for displacement, and then vacuum was applied to-0.1 MPa, and 350 parts of deionized water, 0.2 part of basic calcium phosphate, 0.1 part of azobisisovaleronitrile, 100 parts of vinyl chloride, 10 parts of emulsified glycidyl methacrylate (composition comprising 10 parts of glycidyl methacrylate, 0.05 part of emulsifier, 200 parts of deionized water), and 0.3 part of buffer (ammonium bicarbonate) were added to the polymerization vessel. Turning on a stirrer, turning on a rotating speed to 300rmp, stirring for 25 minutes, turning on an oil bath switch, heating to 10 ℃, starting timing reaction, cooling the reaction kettle to stop reaction when the pressure in the reaction kettle is reduced to 0.2MPa, reducing the stirring rotating speed, opening a bottom valve for discharging, and sequentially cleaning with deionized water, centrifuging and drying to obtain the hydrophilic vinyl chloride copolymer resin.
Example 10
After the polymerization vessel was sealed, nitrogen was used for substitution, and then vacuum was applied to-0.1 MPa, 200 parts of deionized water, 0.15 part of ethylene-maleic anhydride copolymer, 0.8 part of azobisisovaleronitrile, 70 parts of vinyl chloride, 30 parts of emulsified glycidyl methacrylate, and 0.15 part of buffer (ammonium bicarbonate) were added to the polymerization vessel. Turning on a stirrer, turning on a rotating speed to 300rmp, stirring for 25 minutes, turning on an oil bath switch, heating to 10 ℃, starting timing reaction, cooling the reaction kettle to stop reaction when the pressure in the reaction kettle is reduced to 0.2MPa, reducing the stirring rotating speed, opening a bottom valve for discharging, and sequentially cleaning with deionized water, centrifuging and drying to obtain the hydrophilic vinyl chloride copolymer resin.
The foregoing description is only of the individual embodiments of the present invention, and the present invention is not limited to the embodiments, but may be modified or substituted for some of the technical features described in the embodiments described above by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for preparing hydrophilic vinyl chloride copolymer resin, comprising the following steps:
(1) Sealing the polymerization kettle, replacing with nitrogen, and vacuumizing to-0.1 MPa;
(2) Adding deionized water, a dispersing agent, an initiator, vinyl chloride, glycidyl methacrylate and a buffering agent into a polymerization kettle for free radical copolymerization reaction; the temperature of the copolymerization reaction is 10-57.5 ℃; the step (2) comprises the following components in parts by weight: 50-100 parts of chloroethylene; 1-30 parts of glycidyl methacrylate; 0.05-1.2 parts of an initiator; 0.02-0.2 parts of dispersing agent; 0.01-0.3 parts of buffering agent; 100-500 parts of deionized water; the glycidyl methacrylate is emulsified glycidyl methacrylate; the emulsified glycidyl methacrylate per 1 part comprises: 1 part of glycidyl methacrylate, 0.005-0.01 part of emulsifier, and 3-20 parts of deionized water, wherein the emulsifier is sodium dodecyl benzene sulfonate; adding emulsified glycidyl methacrylate in the middle and early stages of the copolymerization reaction; the dispersing agent is one or more of gelatin, cellulose ethers, partially alcoholysis polyvinyl alcohol, styrene-maleic anhydride copolymer, magnesium hydroxide, basic calcium phosphate and calcium carbonate;
(3) And when the pressure in the reaction kettle is reduced to 0.1-0.3 MPa, cooling the reaction kettle to stop the reaction, reducing the stirring rotation speed, opening a bottom valve for discharging, washing with deionized water, centrifuging and drying to obtain the hydrophilic vinyl chloride copolymer resin.
2. The method according to claim 1, wherein the rotational speed of the copolymerization in the step (2) is 300 to 3000rmp.
3. The method of claim 1, wherein the partial alcoholysis has an alcoholysis degree of 40% -85%.
4. A hydrophilic vinylchloride copolymer resin prepared by the preparation method according to any one of claims 1 to 3, characterized by comprising, in parts by mass:
50-100 parts of chloroethylene;
1-30 parts of glycidyl methacrylate;
0.05-1.2 parts of an initiator;
0.02-0.2 parts of dispersing agent;
0.01-0.3 parts of buffering agent;
100-500 parts of deionized water; the glycidyl methacrylate is emulsified glycidyl methacrylate; the emulsified glycidyl methacrylate per 1 part comprises: 1 part of glycidyl methacrylate, 0.005-0.01 part of emulsifier and 3-20 parts of deionized water, wherein the emulsifier is sodium dodecyl benzene sulfonate.
5. The hydrophilic vinylchloride copolymer resin according to claim 4, wherein the initiator comprises one or more of azobisisobutyronitrile, azobisisovaleronitrile, di (2-ethylhexyl) peroxydicarbonate, and cumyl peroxyneodecanoate.
6. The hydrophilic vinylchloride copolymer resin according to claim 4, wherein the buffering agent is one or more of ammonium bicarbonate and sodium bicarbonate.
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