CN118955956B - Polyvinyl chloride high impact modifier and preparation method thereof - Google Patents
Polyvinyl chloride high impact modifier and preparation method thereof Download PDFInfo
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- CN118955956B CN118955956B CN202411453371.5A CN202411453371A CN118955956B CN 118955956 B CN118955956 B CN 118955956B CN 202411453371 A CN202411453371 A CN 202411453371A CN 118955956 B CN118955956 B CN 118955956B
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- 239000004609 Impact Modifier Substances 0.000 title claims abstract description 74
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 60
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011257 shell material Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 229920001577 copolymer Polymers 0.000 claims description 42
- 229920000858 Cyclodextrin Polymers 0.000 claims description 39
- 239000001116 FEMA 4028 Substances 0.000 claims description 21
- 229960004853 betadex Drugs 0.000 claims description 21
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 108010064470 polyaspartate Proteins 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- LNQHREYHFRFJAU-UHFFFAOYSA-N bis(2,5-dioxopyrrolidin-1-yl) pentanedioate Chemical compound O=C1CCC(=O)N1OC(=O)CCCC(=O)ON1C(=O)CCC1=O LNQHREYHFRFJAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- 239000004709 Chlorinated polyethylene Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 7
- 239000008116 calcium stearate Substances 0.000 description 7
- 235000013539 calcium stearate Nutrition 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/16—Cyclodextrin; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a polyvinyl chloride high impact modifier and a preparation method thereof, belonging to the field of high polymer compound compositions. The raw materials of the polyvinyl chloride high impact modifier comprise a modified cyclodextrin inner core and a shell material, wherein the mass ratio of the modified cyclodextrin inner core to the shell material is 6.5-7.5:4. The impact modifier can effectively improve the impact resistance of a polyvinyl chloride material at low temperature, and the impact resistance of a test sample at 0 ℃ to 20 ℃ to 40 ℃ is 45.5 KJ/m 2 at 0 ℃ to 46.3KJ/m 2 at 20 ℃ to 41.3KJ/m 2 at 40 ℃ according to the method in GB/T1043.1-2008.
Description
Technical Field
The invention relates to a polyvinyl chloride high impact modifier and a preparation method thereof, belonging to the field of high polymer compound compositions.
Background
Polyvinyl chloride (PVC) hard products have the characteristics of high strength, high hardness, flame resistance, corrosion resistance, insulation and the like, and are widely applied to various industries by virtue of good physical properties, chemical properties, low price and the like. However, the single hard PVC product has low notch impact strength, poor toughness and easy brittle fracture when impacted, so that an impact modifier needs to be added in a processing formula to obtain enough impact performance so as to achieve the purposes of toughening and reinforcing.
At present, the method for improving the impact performance of PVC hard products almost entirely adopts a blending toughening method, namely, various types of modifiers are added into PVC resin to improve the toughness of the products, and the method belongs to one of physical modification, and can lead to the phenomena of poor resin dispersibility, poor auxiliary agent absorption, uneven plasticization, low toughening efficiency and the like. Therefore, it is necessary to develop a special high impact modifier for PVC having high hardness and high toughness.
Chlorinated Polyethylene (CPE) belongs to a rubber elastomer network polymer, and the modification mechanism is that a network is formed in a PVC material, and the Chlorinated Polyethylene (CPE) is uniformly distributed in PVC resin by virtue of the mixing action of a processing machine, so that the processing melt viscosity of PVC can be reduced, and when PVC and CPE are blended, the impact strength of a profile is correspondingly increased along with the increase of the consumption of the CPE, but the tensile strength is reduced to a certain extent.
The ACR type impact agent belongs to a 'core-shell' structural copolymer, and consists of two parts, wherein the core of the ACR type impact agent is a low-crosslinking acrylate rubber polymer, can be uniformly dispersed into a PVC substrate, and can interact with the PVC substrate. Under the action of heat, the ACR impact modifier has small elastic deformation and low dimensional change rate after the profile is heated, and during proportioning processing, the ACR impact modifier has wider processing range and obviously improved surface finish of the profile compared with a CPE system.
In practical applications, it is found that the impact modifier itself has a low-temperature property, which is firstly manifested by a decrease in elongation of the material at low temperature, and thus a more serious decrease in impact resistance at low temperature, and after quenching in low-temperature environment, a decrease in impact resistance at normal temperature.
In summary, although the impact modifier in the prior art can improve the impact resistance of the material, it is limited to the impact resistance at normal temperature, and when the material is exposed to a low temperature environment, the elongation and thus the impact resistance are greatly reduced, and when the material is heated suddenly in a low temperature environment, the impact resistance at normal temperature is reduced, and the initial impact resistance cannot be recovered.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and uses cyclodextrin as the inner core of the impact modifier, carries out special treatment on the cyclodextrin, and then uses the specially treated methyl methacrylate-ethyl acrylate copolymer as the shell to finally prepare the impact modifier, so that the impact resistance of the material at normal temperature can be improved, the impact resistance of the material at low temperature can be improved, the impact resistance of the material at normal temperature can be better kept after the impact is suddenly heated in a low-temperature environment, and the larger elongation rate can be kept.
In order to solve the technical problems, the invention adopts the following technical scheme:
the polyvinyl chloride high impact modifier is characterized in that raw materials of the polyvinyl chloride high impact modifier comprise a modified cyclodextrin inner core and a modified cyclodextrin outer shell material, and the mass ratio of the modified cyclodextrin inner core to the modified cyclodextrin outer shell material is 6.5-7.5:4.
The following is a further improvement of the above technical scheme:
The preparation method of the modified cyclodextrin core comprises the steps of mixing 2-amino-beta-cyclodextrin with deionized water, stirring to enable the 2-amino-beta-cyclodextrin to be completely dissolved to obtain cyclodextrin aqueous solution, adding sodium polyphosphate into the cyclodextrin aqueous solution, controlling stirring temperature to be 1-3 ℃ by using an ice water bath, stirring for 170-190min, adjusting pH to be 5.1-5.3, adding bissuccinimidyl glutarate, continuously controlling stirring temperature to be 1-3 ℃ by using the ice water bath, stirring for 14.5-15.5h, dialyzing and drying a product in the deionized water after stirring is completed to obtain the modified cyclodextrin core;
The mass ratio of the 2-amino-beta-cyclodextrin to the deionized water to the sodium polyphosphate to the disuccinimidyl glutarate is 45-55:450-550:0.9-1.1:32-37;
the preparation method of the shell material comprises the steps of mixing methyl methacrylate-ethyl acrylate copolymer with toluene, stirring for 13-17min, adding polyaspartic acid ester after stirring is completed, continuously stirring for 13-17min, adding sodium methoxide after stirring is completed, controlling the temperature to be 115-135 ℃, stirring for 7.5-8.5h, and removing toluene through decompression after stirring is completed to obtain the shell material;
the mass ratio of the methyl methacrylate-ethyl acrylate copolymer to the toluene to the polyaspartic acid ester to the sodium methoxide is 14-16:70-80:6.5-7.5:0.9-1.1.
In the preparation method of the shell material, in the methyl methacrylate-ethyl acrylate copolymer, the mass ratio of the methyl methacrylate monomer to the ethyl acrylate monomer is 5.5-6.5:4.
In the preparation method of the shell material, the density of the polyaspartic acid is 1.22g/cm 3.
In the preparation method of the shell material, the density of the methyl methacrylate-ethyl acrylate copolymer is 0.915-0.918g/cm 3.
The preparation method of the high impact modifier comprises the steps of controlling the temperature to be 172-178 ℃, heating a shell material to a molten state to obtain shell liquid for standby, then placing a modified cyclodextrin inner core in a fluidized bed, granulating the modified cyclodextrin inner core by using the shell liquid under the nitrogen atmosphere, and cooling to obtain particles, namely the high impact modifier.
Compared with the prior art, the invention has the following beneficial effects:
The impact modifier can effectively improve the impact resistance of the polyvinyl chloride material, and has the impact strength of 52.7-54.1KJ/m 2 according to the method in GB/T1043.1-2008;
The impact modifier can effectively improve the impact resistance of a polyvinyl chloride material at low temperature, and the impact resistance of a sample at 0 ℃ to 20 ℃ to 40 ℃ is tested according to the method in GB/T1043.1-2008, the impact resistance at 0 ℃ is 45.5 to 46.3KJ/m 2, the impact resistance at 20 ℃ to 20 ℃ is 39.8 to 41.3KJ/m 2, and the impact resistance at 40 ℃ to 40 ℃ is 33.6 to 35.5KJ/m 2;
The impact modifier can ensure that the material still keeps higher impact resistance after being subjected to quenching in a low-temperature environment, a sample is placed for 4 hours at 0 ℃ to 20 ℃ and 40 ℃ respectively, the sample is immediately placed in an oven with constant temperature of 80 ℃ for quenching after the completion of the placing, the quenching time is 60min, the sample is naturally cooled to room temperature after the completion of the quenching, then the test is carried out, the impact strength of the material is 48.1-48.8KJ/m 2 after the quenching at 0 ℃, the impact strength of the material is 45.1-45.9KJ/m 2 after the quenching at 20 ℃, and the impact strength of the material is 41.7-42.6KJ/m 2 after the quenching at 40 ℃;
The impact modifier can effectively improve the breaking elongation of a polyvinyl chloride material, can ensure that the material keeps higher breaking elongation in a low-temperature environment, and can test the breaking elongation of a sample at normal temperature according to the method in GB/T528-2009, and the breaking elongation of the sample at 0 ℃ -20 ℃ -40 ℃ is 446-453%, the breaking elongation at 0 ℃ is 429-435%, the breaking elongation at-20 ℃ is 413-422%, and the breaking elongation at-40 ℃ is 359-377 respectively;
the impact modifier can keep higher transparency and lower haze of polyvinyl chloride, and the transparency and the haze of a test sample are 91.5-92.2% and 4.6-5.5% according to the method in GB/T2410-2008;
The impact modifier can enable polyvinyl chloride to have higher strength, test the bending strength of a sample according to the method in GB/T9341-2008, test the tensile strength of the sample according to the method in GB/T1040.1-2018, and the bending strength is 90.6-91.5MPa and the tensile strength is 65.4-66.1MPa.
Detailed Description
Example 1
The raw materials of the polyvinyl chloride high impact modifier comprise a modified cyclodextrin inner core and a shell material, wherein the mass ratio of the modified cyclodextrin inner core to the shell material is 7:4;
the preparation method of the modified cyclodextrin core comprises the following steps:
Mixing 2-amino-beta-cyclodextrin with deionized water, stirring to completely dissolve the 2-amino-beta-cyclodextrin to obtain a cyclodextrin aqueous solution, adding sodium polyphosphate into the cyclodextrin aqueous solution, controlling the stirring temperature to be 2 ℃ by using an ice water bath, stirring for 180min, adjusting the pH to be 5.2 after stirring, adding bissuccinimidyl glutarate, continuously controlling the stirring temperature to be 2 ℃ by using an ice water bath, stirring for 15h, dialyzing and drying a product in deionized water after stirring to obtain a modified cyclodextrin core;
The mass ratio of the 2-amino-beta-cyclodextrin to the deionized water to the sodium polyphosphate to the disuccinimidyl glutarate is 50:500:1:35.
The preparation method of the shell material comprises the following steps:
Mixing methyl methacrylate-ethyl acrylate copolymer with toluene, stirring for 15min, adding polyaspartic acid ester after stirring is completed, continuing stirring for 15min, adding sodium methoxide after stirring is completed, controlling the temperature to be 125 ℃, stirring for 8h, and removing toluene through decompression after stirring is completed to obtain a shell material;
the mass ratio of the methyl methacrylate-ethyl acrylate copolymer to the toluene to the polyaspartic acid ester to the sodium methoxide is 15:75:7:1;
In the methyl methacrylate-ethyl acrylate copolymer, the mass ratio of the methyl methacrylate monomer to the ethyl acrylate monomer is 6:4;
The density of the methyl methacrylate-ethyl acrylate copolymer is 0.917g/cm 3;
the density of the polyaspartic acid is 1.22g/cm 3.
The preparation method of the high impact modifier comprises the following steps:
And controlling the temperature to 175 ℃, heating the shell material to a molten state to obtain shell liquid for standby, then placing the modified cyclodextrin core in a fluidized bed, granulating the modified cyclodextrin core by using the shell liquid under the nitrogen atmosphere, and cooling to obtain the granules, namely the high impact modifier.
Example 2
The raw materials of the polyvinyl chloride high impact modifier comprise a modified cyclodextrin inner core and a shell material, wherein the mass ratio of the modified cyclodextrin inner core to the shell material is 6.5:4;
the preparation method of the modified cyclodextrin core comprises the following steps:
Mixing 2-amino-beta-cyclodextrin with deionized water, stirring to completely dissolve the 2-amino-beta-cyclodextrin to obtain a cyclodextrin aqueous solution, adding sodium polyphosphate into the cyclodextrin aqueous solution, controlling the stirring temperature to be 1 ℃ by using an ice water bath, stirring for 170min, adjusting the pH to be 5.1 after stirring, adding bissuccinimidyl glutarate, continuously controlling the stirring temperature to be 1 ℃ by using an ice water bath, stirring for 14.5h, dialyzing and drying a product in deionized water after stirring to obtain a modified cyclodextrin core;
The mass ratio of the 2-amino-beta-cyclodextrin to the deionized water to the sodium polyphosphate to the disuccinimidyl glutarate is 45:450:0.9:32.
The preparation method of the shell material comprises the following steps:
mixing methyl methacrylate-ethyl acrylate copolymer with toluene, stirring for 13min, adding polyaspartic acid ester after stirring is completed, continuing stirring for 17min, adding sodium methoxide after stirring is completed, controlling the temperature to be 115 ℃, stirring for 8.5h, and removing toluene by decompression after stirring is completed to obtain a shell material;
The mass ratio of the methyl methacrylate-ethyl acrylate copolymer to the toluene to the polyaspartic acid ester to the sodium methoxide is 14:70:6.5:0.9;
In the methyl methacrylate-ethyl acrylate copolymer, the mass ratio of the methyl methacrylate monomer to the ethyl acrylate monomer is 5.5:4;
The density of the methyl methacrylate-ethyl acrylate copolymer is 0.915g/cm 3;
the density of the polyaspartic acid is 1.22g/cm 3.
The preparation method of the high impact modifier comprises the following steps:
and controlling the temperature to 172 ℃, heating the shell material to a molten state to obtain shell liquid for standby, then placing the modified cyclodextrin core in a fluidized bed, granulating the modified cyclodextrin core by using the shell liquid under the nitrogen atmosphere, and cooling to obtain the granules, namely the high impact modifier.
Example 3
The raw materials of the polyvinyl chloride high impact modifier comprise a modified cyclodextrin inner core and a shell material, wherein the mass ratio of the modified cyclodextrin inner core to the shell material is 7.5:4;
the preparation method of the modified cyclodextrin core comprises the following steps:
mixing 2-amino-beta-cyclodextrin with deionized water, stirring to completely dissolve the 2-amino-beta-cyclodextrin to obtain a cyclodextrin aqueous solution, adding sodium polyphosphate into the cyclodextrin aqueous solution, controlling the stirring temperature to be 3 ℃ by using an ice water bath, stirring for 190min, adjusting the pH to be 5.3 after stirring, adding bissuccinimidyl glutarate, continuously controlling the stirring temperature to be 3 ℃ by using an ice water bath, stirring for 15.5h, dialyzing and drying a product in deionized water after stirring to obtain a modified cyclodextrin core;
The mass ratio of the 2-amino-beta-cyclodextrin to the deionized water to the sodium polyphosphate to the disuccinimidyl glutarate is 55:550:1.1:37.
The preparation method of the shell material comprises the following steps:
Mixing methyl methacrylate-ethyl acrylate copolymer with toluene, stirring for 17min, adding polyaspartic acid ester after stirring, continuing stirring for 13min, adding sodium methoxide after stirring, controlling the temperature to be 135 ℃, stirring for 7.5h, and removing toluene by decompression after stirring to obtain a shell material;
The mass ratio of the methyl methacrylate-ethyl acrylate copolymer to the toluene to the polyaspartic acid ester to the sodium methoxide is 16:80:7.5:1.1;
In the methyl methacrylate-ethyl acrylate copolymer, the mass ratio of the methyl methacrylate monomer to the ethyl acrylate monomer is 6.5:4;
The density of the methyl methacrylate-ethyl acrylate copolymer is 0.918g/cm 3;
the density of the polyaspartic acid is 1.22g/cm 3.
The preparation method of the high impact modifier comprises the following steps:
And controlling the temperature to 175 ℃, heating the shell material to a molten state to obtain shell liquid for standby, then placing the modified cyclodextrin core in a fluidized bed, granulating the modified cyclodextrin core by using the shell liquid under the nitrogen atmosphere, and cooling to obtain the granules, namely the high impact modifier.
Comparative example 1
Unlike example 1, the step of preparing a modified cyclodextrin core was omitted, unmodified 2-amino- β -cyclodextrin was used as a core, and the impact modifier was prepared by fluidized bed granulation with the amount maintained.
Comparative example 2
Unlike example 1, the step of preparing a polymer shell was omitted, and an impact modifier was prepared by fluidized bed granulation using an untreated methyl methacrylate-ethyl acrylate copolymer as a shell material, with the amount remaining unchanged;
in the methyl methacrylate-ethyl acrylate copolymer, the mass ratio of the methyl methacrylate monomer to the ethyl acrylate monomer is 6:4.
Test example 1 impact modifier impact resistance test at Normal temperature
The samples were prepared according to the method in GB/T1043.1-2008, the raw materials in the samples comprise polyvinyl chloride, an impact modifier, calcium stearate and polyethylene wax, the mass ratio of the components in the samples is 1000:50:12:3, then the impact resistance of the samples of examples 1-3 and comparative examples 1-2 at normal temperature (23 ℃) is tested according to the method in GB/T1043.1-2008, and the results are shown in Table 1.
TABLE 1
Examples 1-3 impact modifiers were prepared using specially treated cyclodextrin as the inner core of the impact modifier and then specially treated methyl methacrylate-ethyl acrylate copolymer as the outer shell, and the impact modifier was prepared to give higher impact strength to polyvinyl chloride;
Comparative example 1 omits the step of preparing a modified cyclodextrin core, and uses unmodified 2-amino-beta-cyclodextrin as a core, so that untreated cyclodextrin core can cause the impact strength of polyvinyl chloride to be greatly reduced;
Comparative example 2 using untreated methyl methacrylate-ethyl acrylate copolymer as the shell material, untreated methyl methacrylate-ethyl acrylate copolymer resulted in some decrease in impact strength of polyvinyl chloride.
Test example 2 impact modifier impact resistance test at Low temperature
The samples were prepared according to the method in GB/T1043.1-2008, the raw materials in the samples comprise polyvinyl chloride, an impact modifier, calcium stearate and polyethylene wax, the mass ratio of the components in the samples is 1000:50:12:3, then the impact resistance of the samples of examples 1-3 and comparative examples 1-2 at 0 ℃, -20 ℃ and-40 ℃ is tested according to the method in GB/T1043.1-2008, and the results are shown in Table 2.
TABLE 2
Examples 1-3 impact modifiers were prepared using specially treated cyclodextrin as the inner core of the impact modifier and then specially treated methyl methacrylate-ethyl acrylate copolymer as the outer shell, and the impact modifier was prepared to maintain high impact strength of polyvinyl chloride in a low temperature environment;
Comparative example 1 omits the step of preparing a modified cyclodextrin core, and uses unmodified 2-amino-beta-cyclodextrin as a core, so that untreated cyclodextrin core can cause the impact strength of polyvinyl chloride to be greatly reduced in a low-temperature environment;
comparative example 2 using untreated methyl methacrylate-ethyl acrylate copolymer as a shell material, untreated methyl methacrylate-ethyl acrylate copolymer resulted in a certain decrease in impact strength of polyvinyl chloride in low temperature environment.
Test example 3 impact resistance test of impact modifier after shock heating in low temperature Environment
According to the method in GB/T1043.1-2008, samples are prepared, wherein raw materials in the samples comprise polyvinyl chloride, an impact modifier, calcium stearate and polyethylene wax, the mass ratio of the components in the samples is 1000:50:12:3, then according to the method in GB/T1043.1-2008, the samples of test examples 1-3 and comparative examples 1-2 are placed at 0 ℃ -20 ℃ and 40 ℃ for 4 hours respectively, after the placement is completed, the samples are immediately placed in an oven with constant temperature of 80 ℃ for quenching, the quenching time is 60 minutes, after the quenching is completed, the samples are naturally cooled to room temperature, and then the impact resistance of the samples at normal temperature (23 ℃) is tested, and the results are shown in Table 3.
TABLE 3 Table 3
Examples 1-3 impact modifiers were prepared by using specially treated cyclodextrin as the inner core of the impact modifier and then specially treated methyl methacrylate-ethyl acrylate copolymer as the outer shell, and the finally prepared impact modifier can maintain high impact strength of polyvinyl chloride after it is quenched in a low temperature environment;
Comparative example 1 omitted the step of preparing a modified cyclodextrin core, and the unmodified 2-amino- β -cyclodextrin was used as the core, which resulted in a greater decrease in impact strength after the polyvinyl chloride was quenched in a low temperature environment;
Comparative example 2 using untreated methyl methacrylate-ethyl acrylate copolymer as the shell material, untreated methyl methacrylate-ethyl acrylate copolymer resulted in a certain decrease in impact strength after the polyvinyl chloride was quenched in a low temperature environment.
Test example 4 impact modifier impact on polyvinyl chloride elongation
The samples were prepared according to the method in GB/T528-2009, the raw materials in the samples comprise polyvinyl chloride, an impact modifier, calcium stearate and polyethylene wax, the mass ratio of the components in the samples is 1000:50:12:3, the samples of examples 1-3 and comparative examples 1-2 were tested for elongation at break at normal temperature (23 ℃) according to the method in GB/T528-2009, and the samples of examples 1-3 and comparative examples 1-2 were further tested for elongation at break at 0 ℃, -20 ℃, -40 ℃ respectively, and the results are shown in Table 4.
TABLE 4 Table 4
Examples 1-3 impact modifiers were prepared using specially treated cyclodextrin as the core of the impact modifier and then specially treated methyl methacrylate-ethyl acrylate copolymer as the shell, the impact modifier was prepared to give the polyvinyl chloride a higher elongation at break and still maintain a higher elongation at break in a low temperature environment;
Comparative example 1 omits the step of preparing a modified cyclodextrin core, and uses unmodified 2-amino-beta-cyclodextrin as a core, so that untreated cyclodextrin core can cause lower elongation at break of polyvinyl chloride at normal temperature and larger reduction of elongation at break in low-temperature environment;
comparative example 2 using untreated methyl methacrylate-ethyl acrylate copolymer as a shell material, untreated methyl methacrylate-ethyl acrylate copolymer resulted in lower elongation at break at normal temperature of polyvinyl chloride and some decrease in elongation at break in low temperature environment.
Test example 5 impact modifier test for impact on clarity and haze of polyvinyl chloride
The samples were prepared according to the method in GB/T2410-2008, the raw materials in the samples comprise polyvinyl chloride, an impact modifier, calcium stearate and polyethylene wax, the mass ratio of the components in the samples is 1000:50:12:3, and then the samples of examples 1-3 and comparative examples 1-2 were tested for transparency and haze according to the method in GB/T2410-2008, respectively, and the results are shown in Table 5.
TABLE 5
Examples 1-3 impact modifiers were prepared using specially treated cyclodextrin as the inner core of the impact modifier and then specially treated methyl methacrylate-ethyl acrylate copolymer as the outer shell, the impact modifier being prepared to give the polyvinyl chloride a higher clarity and lower haze;
Comparative example 1 omits the step of preparing a modified cyclodextrin core, and uses unmodified 2-amino-beta-cyclodextrin as a core, so that untreated cyclodextrin core can cause the transparency of polyvinyl chloride to be reduced to a certain extent and the haze to be increased to a certain extent;
Comparative example 2 using untreated methyl methacrylate-ethyl acrylate copolymer as the shell material, untreated methyl methacrylate-ethyl acrylate copolymer resulted in a greater degree of decrease in transparency and a greater degree of increase in haze of polyvinyl chloride.
Test example 6 impact modifier impact on polyvinyl chloride strength
Preparing a sample according to the method in GB/T9341-2008, wherein the raw materials in the sample comprise polyvinyl chloride, an impact modifier, calcium stearate and polyethylene wax, the mass ratio of the components in the sample is 1000:50:12:3, and then testing the bending strength of the samples of examples 1-3 and comparative examples 1-2 respectively according to the method in GB/T9341-2008;
Preparing a sample according to the method in GB/T1040.1-2018, wherein the raw materials in the sample comprise polyvinyl chloride, an impact modifier, calcium stearate and polyethylene wax, the mass ratio of the components in the sample is 1000:50:12:3, and then respectively testing the tensile strength of the samples in examples 1-3 and comparative examples 1-2 according to the method in GB/T1040.1-2018;
The results are shown in Table 6.
TABLE 6
Examples 1-3 impact modifiers were prepared using specially treated cyclodextrin as the inner core of the impact modifier and then specially treated methyl methacrylate-ethyl acrylate copolymer as the outer shell, and the impact modifiers were prepared to give the polyvinyl chloride higher flexural and tensile strengths;
Comparative example 1 omits the step of preparing a modified cyclodextrin core, and uses unmodified 2-amino-beta-cyclodextrin as a core, so that untreated cyclodextrin core can cause the bending strength of polyvinyl chloride to be reduced to a certain extent and the tensile strength to be reduced to a larger extent;
Comparative example 2 using untreated methyl methacrylate-ethyl acrylate copolymer as the shell material, untreated methyl methacrylate-ethyl acrylate copolymer resulted in a significant decrease in flexural strength and a certain decrease in tensile strength of the polyvinyl chloride.
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| CN101987903B (en) * | 2010-04-08 | 2012-01-11 | 罗德艾博(厦门)塑胶科技有限公司 | Impact resistance modifying agent of PVC-M tubing and pipe fitting |
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