CN118048043A - High-tensile-strength impact modifier for polyvinyl chloride and preparation method thereof - Google Patents
High-tensile-strength impact modifier for polyvinyl chloride and preparation method thereof Download PDFInfo
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 67
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 66
- 239000004609 Impact Modifier Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229920005610 lignin Polymers 0.000 claims abstract description 81
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 37
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 33
- 239000004952 Polyamide Substances 0.000 claims abstract description 31
- 229920002647 polyamide Polymers 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 29
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000012948 isocyanate Substances 0.000 claims description 22
- 150000002513 isocyanates Chemical class 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 14
- 229910021485 fumed silica Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyethylene Polymers 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 4
- 229920000573 polyethylene Polymers 0.000 abstract description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000088 plastic resin Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XCEDYBCDZCQLER-UHFFFAOYSA-N 2-methylbuta-1,3-diene;prop-2-enenitrile;styrene Chemical compound C=CC#N.CC(=C)C=C.C=CC1=CC=CC=C1 XCEDYBCDZCQLER-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A high-tensile-strength impact modifier for polyvinyl chloride and a preparation method thereof belong to the technical field of high polymer materials, and the high-tensile-strength impact modifier for polyvinyl chloride is viscous liquid and mainly comprises nitrile rubber coated lignin, modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene; the high-tensile-strength impact modifier for polyvinyl chloride is prepared from 100 parts of polyvinyl chloride, 5 parts of high-tensile-strength impact modifier, 2 parts of calcium-zinc stabilizer and 1 part of polyethylene wax according to a test formula, wherein the tensile strength is 60.8-62.5 MPa, the bending strength is 86.9-88.2 MPa, the elongation at break is 385-412%, the notch impact strength is 63.8-65.1 KJ/m 2, and the Vicat softening temperature is 87.3-88.1 ℃.
Description
Technical Field
The invention relates to a high-tensile-strength impact modifier for polyvinyl chloride and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Polyvinyl chloride (PVC) plastic resin is inexpensive, has excellent outdoor aging resistance and flame retardancy, and has been the second most versatile plastic resin with consumption inferior to polyethylene. The world productivity has reached 6500 ten thousand tons, and nearly 90% of polyvinyl chloride is mainly used as hard materials, but the inherent structure of polyvinyl chloride determines that inherent defects exist when the polyvinyl chloride is used as hard materials, and the main manifestation is: the melt strength is low, and the processability is poor; the impact resistance is poor, and the notch impact strength of the hard PVC is only 2kJ/m 2 -5 kJ/m 2; the tensile strength is low. Polyvinyl chloride has therefore become the most modified plastic resin, where how to maximize its impact resistance without reducing its tensile strength, while improving other properties has been a hotspot for PVC modification.
CN104231151a discloses a large particle size acrylic ester impact modifier for polyvinyl chloride and a preparation method thereof, wherein the impact modifier is a large particle size core-shell polyacrylate copolymer. The main components of the water-based paint comprise deionized water, polyvinyl alcohol, butyl acrylate, methyl methacrylate and the like. According to the invention, polyvinyl alcohol is used as a protective colloid through a seed emulsion polymerization process, seed emulsion with a core layer consisting of butyl acrylate, isobornyl methacrylate, methyl methacrylate and a cross-linking agent is synthesized, and a shell layer is formed by cladding butyl acrylate, styrene, isobornyl methacrylate, methyl methacrylate and the cross-linking agent. The particle size of the grafted copolymer prepared by the invention is larger than 600nm, so that the problem of compatibility between the acrylic ester impact modifier and the polyvinyl chloride is solved, and the acrylic ester impact modifier is rapidly and uniformly dispersed in the polyvinyl chloride particles, thereby effectively toughening the polyvinyl chloride product. As a result of the test disclosed in the patent, the impact strength of the polyvinyl chloride is improved relatively greatly, but the tensile strength is not improved substantially.
CN102417674a discloses a polyvinyl chloride high impact modifier and a preparation method thereof, the polyvinyl chloride impact modifier is a ternary graft copolymer resin of acrylonitrile-isoprene-styrene, and is composed of a rubber component and a graft layer on the outer layer of the rubber component, the rubber component is a copolymer of isoprene and styrene, the mass of the rubber component accounts for 40-80% of the total mass of the copolymer resin, and the mass ratio of isoprene to styrene is 75:25; the grafting layer is a copolymer of styrene and acrylonitrile, the mass of the grafting layer accounts for 20-60% of the total mass of the copolymer resin, and the mass ratio of the styrene to the acrylonitrile is 60:40-40:60. The high impact modifier obtained by the patent has very limited improvement on the toughness of the polyvinyl chloride, the impact resistance is not greatly improved, and the tensile strength is not improved at all.
From the above discussion, it can be seen that the existing polyvinyl chloride impact modifier still has the defect that it is difficult to improve the tensile strength and the impact strength of polyvinyl chloride at the same time, so that developing a high tensile strength impact modifier for polyvinyl chloride is very important to improve the use value of polyvinyl chloride deeply.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a high-tensile-strength impact modifier for polyvinyl chloride and a preparation method thereof, which realize the following aims: a high tensile strength impact modifier capable of improving both tensile strength and impact strength of polyvinyl chloride is prepared.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
The high-tensile-strength impact modifier for the polyvinyl chloride is viscous liquid, and mainly comprises nitrile rubber coated lignin, modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene;
The following is a further improvement of the above technical scheme:
step 1, preparation of nitrile rubber coated lignin
Drying lignin at 90-110 ℃ for 20-30 hours, putting the lignin into a planetary ball mill thoroughly drying and dewatering, adding toluene with the mass of 20-40 wt% of the lignin, controlling the rotating speed to 1500-2200 r/min, grinding to the particle size of 0.01-0.9 mu m, putting the ground lignin slurry into a dry and anhydrous reaction kettle, adding toluene with the mass of 0.8-1.1 times of the lignin slurry, controlling the stirring speed to 3000-6000 r/min, heating and keeping the temperature to 80-95 ℃, slowly dripping isocyanate, continuing to stir at the constant temperature for 6-10 hours after dripping, adding carboxyl-terminated nitrile rubber, continuing to stir and reacting until the mass content of liquid isocyanate groups in the kettle is 0wt%, stopping stirring and cooling to room temperature, centrifuging, and vacuum drying separated solid at 50-80 ℃ for 8-14 hours to obtain nitrile rubber coated lignin;
slowly dropwise adding isocyanate, wherein the adding mass of the isocyanate is 10-35 wt% of the mass of lignin, and the dropping speed is 10-60 g/min;
The isocyanate is one of toluene diisocyanate and diphenylmethane diisocyanate;
The addition amount of the carboxyl-terminated nitrile rubber is 8-20wt% of the lignin;
the carboxyl content of the carboxyl-terminated nitrile rubber is 0.5-0.7 mol/kg, the viscosity at 40 ℃ is 6-11 Pa.s, and the number average molecular weight is 2000-4000 g/mol.
Step 2, preparation of modified nano inorganic powder
Drying nano calcium carbonate and gas-phase silicon dioxide at a high temperature of 100-140 ℃ for 15-22 hours, putting the dried nano calcium carbonate and gas-phase silicon dioxide into a high-speed dispersion kettle, adding absolute ethyl alcohol and vinyl pyrrolidone-vinyl acetate copolymer, controlling the dispersion rate to be 6000-9500 r/min, heating and keeping the temperature to 50-70 ℃ for 5-9 hours, adding 3-diethylenetriamine propyl trimethoxy silane, reducing the dispersion rate to 3500-4500 r/min, keeping the temperature for 8-14 hours, cooling to room temperature, centrifuging, and vacuum drying the obtained solid at 50-70 ℃ for 4-7 hours to obtain modified nano inorganic powder;
The particle size of the nano calcium carbonate is 5-30 nm;
The particle size of the fumed silica is 10-50 nm;
the model of the vinyl pyrrolidone-vinyl acetate copolymer is VA64, and the K value is 26-33;
The material adding mass ratio of the nano calcium carbonate to the fumed silica to the absolute ethyl alcohol to the vinyl pyrrolidone-vinyl acetate copolymer to the 3-diethylenetriamine propyl trimethoxy silane is 10-35:5-20:130-180:0.5-1.2:2-7.
Step 3, preparation of high tensile Strength impact modifier
The preparation method comprises the steps of (1) primarily mixing modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene, then placing the mixture on a high-speed dispersing machine, dispersing the mixture for 16-20 hours at 25000-35000 rpm, then adding nitrile rubber to coat lignin, continuously dispersing the mixture for 10-14 hours, and discharging the mixture to obtain viscous liquid, namely the high-tensile-strength impact modifier;
the mass ratio of the nitrile rubber coated lignin to the modified nano inorganic powder to the hyperbranched polyglycidyl to the amino-terminated hyperbranched polyamide to the hydroxyl-terminated polybutadiene is 10-25:15-40:5-13:10-20:25-35;
the molecular weight of the hyperbranched polyglycidyl is 800-2500 g/mol;
The amino-terminated hyperbranched polyamide has the amino-terminated number of 4-14 mol/mol, the molecular weight of 300-1400 g/mol and the property of yellow liquid;
the hydroxyl value of the hydroxyl-terminated polybutadiene is 50-110 mg KOH/g, the viscosity at 40 ℃ is 1-20 Pa.s, and the molecular weight is 900-4000 g/mol.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the invention, isocyanate is used for modifying the surface of lignin particles, after the hydroxyl groups on the surface of lignin react with the isocyanate, the hydroxyl groups on the surface of lignin are replaced by the isocyanate groups, the polarity of the surface of lignin particles is reduced, the hydrophobicity is enhanced, then the lignin particles and carboxyl-terminated nitrile rubber are subjected to coating reaction under high-speed stirring, and the carboxyl-terminated nitrile rubber and the isocyanate groups on the surface of lignin react chemically in the coating process, so that the chemical coating of the carboxyl-terminated nitrile rubber on the lignin particles is realized. The carboxyl-terminated nitrile rubber has very good compatibility with the polyvinyl chloride, is easy to be uniformly dispersed in a polyvinyl chloride resin matrix, so that lignin can be very well dispersed due to chemical coating, the improvement effect of lignin on the heat resistance and the tensile strength of the polyvinyl chloride can be improved to the greatest extent, the carboxyl-terminated nitrile rubber has very good toughening effect on the polyvinyl chloride, and the impact strength of the polyvinyl chloride can be greatly improved, so that the lignin coated by the carboxyl-terminated nitrile rubber can have the effect of improving the tensile strength and the impact strength at the same time, and the finally obtained high-tensile-strength impact modifier can greatly improve the impact strength and the tensile strength of the polyvinyl chloride;
2. According to the invention, 3-diethylenetriamine propyl trimethoxysilane is used for dispersing and surface modifying nano calcium carbonate and gas-phase silicon dioxide under the dispersion action of a dispersing agent vinyl pyrrolidone-vinyl acetate copolymer, the dispersion efficacy of the vinyl pyrrolidone-vinyl acetate copolymer is relatively strong, the nano calcium carbonate and the gas-phase silicon dioxide can be dispersed to a nano level in an absolute ethyl alcohol solvent, and the nano level single particles and the 3-diethylenetriamine propyl trimethoxysilane are subjected to surface modification reaction, so that the nano level dispersion of the two nano inorganic powder in a high tensile strength impact modifier is ensured, and the nano level dispersion of the nano calcium carbonate and the gas-phase silicon dioxide in a polyvinyl chloride resin matrix in the process of thermally mixing the high tensile strength impact modifier and the polyvinyl chloride is realized, so that the impact modification effect of the two nano inorganic fillers on the polyvinyl chloride is exerted to the greatest extent;
3. The two hyperbranched polymers added in the invention are both polar polymers, the compatibility with polyvinyl chloride is very good, the two substances can form hydrogen bond action with the polyvinyl chloride, the blending free energy can be reduced to approach zero, the addition of the two hyperbranched polymers greatly promotes the compatibility of each component in the high tensile strength impact modifier with the polyvinyl chloride, the components are fully fused in a polyvinyl chloride high molecular chain segment to form a microscopic continuous phase structure, more importantly, a large number of hydroxyl groups and amino groups contained in the hyperbranched polyglycidyl and amino-terminated hyperbranched polyamide can form intermolecular hydrogen bond with methine hydrogen in the polyvinyl chloride to block the sliding among polyvinyl chloride molecular chains, so that the tensile strength of the polyvinyl chloride is improved, in addition, the intermolecular hydrogen bond forms a certain physical crosslinking network, and the network can buffer external impact, so that the impact resistance of the polyvinyl chloride is improved;
4. The hydroxyl-terminated polybutadiene added in the invention is a toughening liquid rubber, the polarity of hydroxyl-terminated promotes the compatibility of the hydroxyl-terminated polybutadiene with hyperbranched polyglycidyl and amino-terminated hyperbranched polyamide, and also promotes the compatibility of the hydroxyl-terminated polybutadiene with polyvinyl chloride, the butadiene-based liquid rubber can form a sea island aggregation form in a polyvinyl chloride resin matrix, the structure can form a stress concentration center, induce the matrix to generate a large number of silver lines and shear bands, and simultaneously can control the development of the silver lines to stop the silver lines in time without developing destructive cracks, and based on the principle, the hydroxyl-terminated polybutadiene can greatly improve the toughness of the polyvinyl chloride and ensure that the polyvinyl chloride has higher impact strength;
5. The high-tensile-strength impact modifier for polyvinyl chloride is prepared from 100 parts of polyvinyl chloride, 5 parts of high-tensile-strength impact modifier, 2 parts of calcium-zinc stabilizer and 1 part of polyethylene wax according to a test formula, wherein the tensile strength is 60.8-62.5 MPa, the bending strength is 86.9-88.2 MPa, the elongation at break is 385-412%, the notch impact strength is 63.8-65.1 KJ/m 2, and the Vicat softening temperature is 87.3-88.1 ℃.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1: high-tensile-strength impact modifier for polyvinyl chloride and preparation method thereof
Step 1, preparation of nitrile rubber coated lignin
Drying lignin at 103 ℃ for 26 hours, putting the lignin into a planetary ball mill for thoroughly drying and dewatering, then adding toluene with the mass of 29wt% of lignin, controlling the rotating speed to 1900 revolutions per minute, grinding the lignin to the particle size of 0.08 mu m, putting the ground lignin slurry into a dry and anhydrous reaction kettle, adding toluene with the mass of 0.9 times of the lignin slurry, controlling the stirring speed to 4700 revolutions per minute, heating and keeping the temperature to 84 ℃, slowly dripping isocyanate, continuing to stir and react for 9 hours at the constant temperature after the dripping is finished, adding carboxyl-terminated nitrile rubber, continuing to stir and react until the mass content of liquid isocyanate groups in the kettle is 0wt%, stopping stirring and cooling to room temperature, then centrifugally separating, and vacuum drying the separated solid at 67 ℃ for 11 hours to obtain the nitrile rubber coated lignin;
Slowly dropwise adding isocyanate, wherein the adding mass of the isocyanate is 29wt% of the mass of lignin, and the dropwise adding speed is 38g/min;
the isocyanate is toluene diisocyanate;
The addition amount of the carboxyl-terminated nitrile rubber is 14 weight percent of the lignin;
The carboxyl content of the carboxyl-terminated nitrile rubber is 0.6mol/kg, the viscosity at 40 ℃ is 8 Pa.s, and the number average molecular weight is 3500g/mol.
Step 2, preparation of modified nano inorganic powder
Drying nano calcium carbonate and gas-phase silicon dioxide at a high temperature of 125 ℃ for 19 hours, then placing the nano calcium carbonate and the gas-phase silicon dioxide into a high-speed dispersion kettle, adding absolute ethyl alcohol and a vinyl pyrrolidone-vinyl acetate copolymer, controlling the dispersion speed to 8600 r/min, heating and keeping the temperature to 65 ℃ for constant-temperature dispersion for 8 hours, adding 3-diethylenetriamine propyl trimethoxy silane, reducing the dispersion speed to 4300 r/min, keeping the temperature for dispersion for 11 hours, cooling to room temperature, centrifuging, and vacuum drying the obtained solid at 65 ℃ for 5 hours to obtain modified nano inorganic powder;
the particle size of the nano calcium carbonate is 20nm;
The particle size of the fumed silica is 30nm;
the model of the vinyl pyrrolidone-vinyl acetate copolymer is VA64, and the K value is 30;
The material feeding mass ratio of the nano calcium carbonate to the fumed silica to the absolute ethyl alcohol to the vinyl pyrrolidone-vinyl acetate copolymer to the 3-diethylenetriamine propyl trimethoxy silane is 23:15:160:0.9:6.
Step 3, preparation of high tensile Strength impact modifier
The preparation method comprises the steps of (1) primarily mixing modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene, then placing the mixture on a high-speed dispersing machine, dispersing for 19 hours at 33000 r/min, then adding nitrile rubber to coat lignin, continuously dispersing for 13 hours, and discharging to obtain viscous liquid, namely the high-tensile-strength impact modifier;
the mass ratio of the nitrile rubber coated lignin to the modified nano inorganic powder to the hyperbranched polyglycidyl to the amino-terminated hyperbranched polyamide to the hydroxyl-terminated polybutadiene is 18:32:11:14:29;
the molecular weight of the hyperbranched polyglycidyl is 2100g/mol;
The amino-terminated hyperbranched polyamide has the amino-terminated number of 11mol/mol, the molecular weight of 950g/mol and a yellow liquid;
The hydroxyl value of the hydroxyl-terminated polybutadiene is 75mg KOH/g, the viscosity at 40 ℃ is 13 Pa.s, and the molecular weight is 3500g/mol.
Example 2: high-tensile-strength impact modifier for polyvinyl chloride and preparation method thereof
Step 1, preparation of nitrile rubber coated lignin
Drying lignin at 90 ℃ for 20 hours, putting the lignin into a planetary ball mill for thoroughly drying and dewatering, then adding toluene with the mass of 20wt% of lignin, controlling the rotating speed to 1500 revolutions per minute, grinding the lignin to the particle size of 0.01 mu m, putting the ground lignin slurry into a dry and anhydrous reaction kettle, adding toluene with the mass of 0.8 times of the lignin slurry, controlling the stirring speed to 3000 revolutions per minute, heating and keeping the temperature to 80 ℃, slowly dripping isocyanate, continuing to stir and react at the constant temperature for 6 hours after the dripping is finished, adding carboxyl-terminated nitrile rubber, continuing to stir and react until the mass content of liquid isocyanate groups in the kettle is 0wt%, stopping stirring and cooling to room temperature, centrifuging, and drying the separated solid in vacuum at 50 ℃ for 8 hours to obtain nitrile rubber coated lignin;
slowly dropwise adding isocyanate, wherein the adding mass of the isocyanate is 10wt% of the mass of lignin, and the dropwise adding speed is 10g/min;
The isocyanate is diphenylmethane diisocyanate;
The addition amount of the carboxyl-terminated nitrile rubber is 8wt% of the lignin mass;
The carboxyl content of the carboxyl-terminated nitrile rubber is 0.5mol/kg, the viscosity at 40 ℃ is 6 Pa.s, and the number average molecular weight is 2000g/mol.
Step 2, preparation of modified nano inorganic powder
Drying nano calcium carbonate and gas-phase silicon dioxide at a high temperature of 100 ℃ for 15 hours, then placing the nano calcium carbonate and the gas-phase silicon dioxide into a high-speed dispersion kettle, then adding absolute ethyl alcohol and a vinyl pyrrolidone-vinyl acetate copolymer, controlling the dispersion speed to 6000 r/min, heating and keeping the temperature to 50 ℃ for constant temperature dispersion for 5 hours, then adding 3-diethylenetriamine propyl trimethoxy silane, reducing the dispersion speed to 3500 r/min, dispersing at the constant temperature for 8 hours, then cooling to room temperature, centrifuging, and drying the obtained solid in vacuum at 50 ℃ for 4 hours to obtain modified nano inorganic powder;
the particle size of the nano calcium carbonate is 5nm;
The particle size of the fumed silica is 10nm;
The model of the vinyl pyrrolidone-vinyl acetate copolymer is VA64, and the K value is 26;
the mass ratio of the nano calcium carbonate to the fumed silica to the anhydrous ethanol to the charging material of the vinyl pyrrolidone-vinyl acetate copolymer to the charging material of the 3-diethylenetriamine propyl trimethoxy silane is 10:5:130:0.5:2.
Step 3, preparation of high tensile Strength impact modifier
The preparation method comprises the steps of (1) primarily mixing modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene, then placing the mixture on a high-speed dispersing machine, dispersing the mixture for 16 hours at 25000 rpm, then adding nitrile rubber to coat lignin, continuously dispersing the mixture for 10 hours, and discharging the mixture to obtain viscous liquid, namely the high-tensile-strength impact modifier;
The mass ratio of the nitrile rubber coated lignin to the modified nano inorganic powder to the hyperbranched polyglycidyl to the amino-terminated hyperbranched polyamide to the hydroxyl-terminated polybutadiene is 10:15:5:10:25;
the molecular weight of the hyperbranched polyglycidyl is 800g/mol;
the amino-terminated hyperbranched polyamide has the amino-terminated number of 4mol/mol, the molecular weight of 300g/mol and a yellow liquid;
The hydroxyl value of the hydroxyl-terminated polybutadiene is 50mg KOH/g, the viscosity at 40 ℃ is 1 Pa.s, and the molecular weight is 900g/mol.
Example 3: high-tensile-strength impact modifier for polyvinyl chloride and preparation method thereof
Step 1, preparation of nitrile rubber coated lignin
Drying lignin at 110 ℃ for 30 hours, putting the lignin into a planetary ball mill for thoroughly drying and dewatering, then adding toluene with the weight of 40 percent of the lignin, controlling the rotating speed to 2200 revolutions per minute, grinding the lignin to the grain diameter of 0.9 mu m, putting the ground lignin slurry into a dry and anhydrous reaction kettle, adding toluene with the weight of 1.1 times of the lignin slurry, controlling the stirring speed to 6000 revolutions per minute, heating and keeping the temperature to 95 ℃, slowly dripping isocyanate, continuing to stir and react at the constant temperature for 10 hours, adding carboxyl terminated nitrile rubber, continuing to stir and react until the mass content of liquid isocyanate groups in the kettle is 0 percent, stopping stirring and cooling to room temperature, centrifuging, and vacuum drying the separated solid at 80 ℃ for 14 hours to obtain nitrile rubber coated lignin;
slowly dropwise adding isocyanate, wherein the adding mass of the isocyanate is 35wt% of the mass of lignin, and the dropwise adding speed is 60g/min;
the isocyanate is toluene diisocyanate;
the addition amount of the carboxyl-terminated nitrile rubber is 20wt% of the lignin mass;
The carboxyl content of the carboxyl-terminated nitrile rubber is 0.7mol/kg, the viscosity at 40 ℃ is 11 Pa.s, and the number average molecular weight is 4000g/mol.
Step 2, preparation of modified nano inorganic powder
Drying nano calcium carbonate and gas-phase silicon dioxide at a high temperature of 140 ℃ for 22 hours, then placing the nano calcium carbonate and the gas-phase silicon dioxide into a high-speed dispersion kettle, adding absolute ethyl alcohol and a vinyl pyrrolidone-vinyl acetate copolymer, controlling the dispersion speed to 9500 r/min, heating and keeping the temperature to 70 ℃ for constant-temperature dispersion for 9 hours, adding 3-diethylenetriamine propyl trimethoxy silane, reducing the dispersion speed to 4500 r/min, dispersing at the constant temperature for 14 hours, cooling to room temperature, centrifuging, and vacuum drying the obtained solid at 70 ℃ for 7 hours to obtain modified nano inorganic powder;
The particle size of the nano calcium carbonate is 30nm;
The particle size of the fumed silica is 50nm;
the model of the vinyl pyrrolidone-vinyl acetate copolymer is VA64, and the K value is 33;
The mass ratio of the nano calcium carbonate to the fumed silica to the anhydrous ethanol to the vinyl pyrrolidone-vinyl acetate copolymer to the 3-diethylenetriamine propyl trimethoxy silane is 35:20:180:1.2:7.
Step 3, preparation of high tensile Strength impact modifier
The preparation method comprises the steps of (1) primarily mixing modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene, then placing the mixture on a high-speed dispersing machine, dispersing for 20 hours at a rotating speed of 35000 r/min, then adding nitrile rubber to coat lignin, continuously dispersing for 14 hours, and discharging to obtain viscous liquid, namely the high-tensile-strength impact modifier;
The mass ratio of the nitrile rubber coated lignin to the modified nano inorganic powder to the hyperbranched polyglycidyl to the amino-terminated hyperbranched polyamide to the hydroxyl-terminated polybutadiene is 25:40:13:20:35;
the molecular weight of the hyperbranched polyglycidyl is 2500g/mol;
The amino-terminated hyperbranched polyamide has the amino-terminated number of 14mol/mol, the molecular weight of 1400g/mol and a yellow liquid;
The hydroxyl-terminated polybutadiene has a hydroxyl number of 110mg KOH/g, a viscosity of 20 Pa.s at 40℃and a molecular weight of 4000g/mol.
Comparative example 1: based on the embodiment 1, the preparation of the nitrile rubber coated lignin in the step 1 is not carried out, and in the preparation of the impact modifier with high tensile strength in the step 3, 18 parts of the nitrile rubber coated lignin is replaced by 18 parts of modified nano inorganic powder in an equivalent way, and the specific operation is as follows:
Step 1, preparing the nitrile rubber coated lignin;
step 2 was performed as in example 1;
step 3, preparation of high tensile Strength impact modifier
The modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene are initially mixed and then are placed on a high-speed dispersing machine to be dispersed for 19 hours at the rotational speed of 33000 r/min and then discharged, and the obtained viscous liquid is the high-tensile-strength impact modifier;
the mass ratio of the modified nano inorganic powder to the hyperbranched polyglycidyl to the amino-terminated hyperbranched polyamide to the hydroxyl-terminated polybutadiene is 50:11:14:29;
the molecular weight of the hyperbranched polyglycidyl is 2100g/mol;
The amino-terminated hyperbranched polyamide has the amino-terminated number of 11mol/mol, the molecular weight of 950g/mol and a yellow liquid;
The hydroxyl value of the hydroxyl-terminated polybutadiene is 75mg KOH/g, the viscosity at 40 ℃ is 13 Pa.s, and the molecular weight is 3500g/mol.
Comparative example 2: based on the example 1, in the preparation of the modified nano inorganic powder in the step 2, the vinyl pyrrolidone-vinyl acetate copolymer is not added, and 0.9 part of the vinyl pyrrolidone-vinyl acetate copolymer is replaced by 0.9 part of absolute ethyl alcohol in an equivalent amount, and the specific operation is as follows:
Step 1, the operation is the same as in example 1;
step 2, preparation of modified nano inorganic powder
Drying nano calcium carbonate and gas-phase silicon dioxide at a high temperature of 125 ℃ for 19 hours, then placing the nano calcium carbonate and the gas-phase silicon dioxide into a high-speed dispersion kettle, adding absolute ethyl alcohol, controlling the dispersion speed to 8600 r/min, heating and keeping the temperature to 65 ℃ for constant-temperature dispersion for 8 hours, adding 3-diethylenetriamine propyl trimethoxy silane, reducing the dispersion speed to 4300 r/min, keeping the temperature for dispersion for 11 hours, cooling to room temperature, centrifuging, and drying the obtained solid at 65 ℃ in vacuum for 5 hours to obtain modified nano inorganic powder;
the particle size of the nano calcium carbonate is 20nm;
The particle size of the fumed silica is 30nm;
The mass ratio of the nano calcium carbonate to the fumed silica to the absolute ethyl alcohol to the 3-diethylenetriamine propyl trimethoxy silane is 23:15:160.9:6;
Step 3 was performed as in example 1.
Comparative example 3: based on example 1, in step 3, the preparation of the high tensile strength impact modifier, without adding hyperbranched polyglycidyl and amino-terminated hyperbranched polyamide, 11 parts of hyperbranched polyglycidyl and 14 parts of amino-terminated hyperbranched polyamide are replaced by 25 parts of hydroxyl-terminated polybutadiene in equal amount, and the specific operation is as follows:
steps 1 and 2 are the same as in example 1;
step 3, preparation of high tensile Strength impact modifier
After preliminary mixing, placing the modified nano inorganic powder and hydroxyl-terminated polybutadiene on a high-speed dispersing machine, dispersing for 19 hours at 33000 r/min, then adding nitrile rubber to coat lignin, continuously dispersing for 13 hours, and discharging to obtain viscous liquid, namely the high-tensile-strength impact modifier;
the mass ratio of the nitrile rubber coated lignin to the modified nano inorganic powder to the hydroxyl-terminated polybutadiene is 18:32:54;
The hydroxyl value of the hydroxyl-terminated polybutadiene is 75mg KOH/g, the viscosity at 40 ℃ is 13 Pa.s, and the molecular weight is 3500g/mol.
Comparative example 4: example 1 based on step 3, preparation of high tensile impact modifier, no hydroxyl-terminated polybutadiene was added, 29 parts of hydroxyl-terminated polybutadiene was replaced with 29 parts of amino-terminated hyperbranched polyamide in equal amounts, and the specific procedure was as follows:
steps 1 and 2 are the same as in example 1;
step 3, preparation of high tensile Strength impact modifier
After preliminary mixing, the modified nano inorganic powder, hyperbranched polyglycidyl and amino-terminated hyperbranched polyamide are placed on a high-speed dispersing machine to be dispersed for 19 hours at the rotating speed of 33000 r/min, then nitrile rubber is added to coat lignin, and the mixture is discharged after being continuously dispersed for 13 hours, so that the obtained viscous liquid is the high-tensile-strength impact modifier;
the mass ratio of the nitrile rubber coated lignin to the modified nano inorganic powder to the hyperbranched polyglycidyl to the amino-terminated hyperbranched polyamide is 18:32:11:43;
the molecular weight of the hyperbranched polyglycidyl is 2100g/mol;
the amino-terminated hyperbranched polyamide has the amino-terminated number of 11mol/mol, the molecular weight of 950g/mol and the property of yellow liquid.
Performance test:
The high tensile strength impact modifiers prepared in examples 1, 2, 3 and comparative examples 1, 2, 3 and 4 were respectively put into a mixer for hot mixing according to 100 parts of polyvinyl chloride, 5 parts of the high tensile strength impact modifier, 2 parts of a calcium zinc stabilizer and 1 part of polyethylene wax, the mixing temperature was controlled to 120 ℃, the stirring speed was 60 revolutions per minute, the mixing time was 25 minutes, and the discharged materials were cooled to room temperature to obtain test samples, and the test samples were prepared and tested for tensile strength, flexural strength, elongation at break, notched impact strength at 23 ℃ and vicat softening point by referring to GB/T1040-2018, GB/T1043.1-2008, GB/T528-2009, GB/T9341-2008, GB/T1633-2000, and the test results are shown in table 1:
TABLE 1
As can be seen from table 1, comparative example 1, in which no nitrile rubber-coated lignin was added, had the worst tensile strength, bending strength and vicat softening point in all examples and comparative examples, and had slightly higher elongation at break and notched impact strength than comparative example 3, indicating that the nitrile rubber-coated lignin had a very significant effect on improving the tensile strength, bending strength and impact strength of polyvinyl chloride, and also had a key effect on improving the heat resistance of polyvinyl chloride; in comparative example 2, the mechanical properties of the polyvinyl chloride are greatly reduced without adding the vinyl pyrrolidone-vinyl acetate copolymer in the preparation of the modified nano inorganic powder, and the Vicat softening point is also obviously reduced, which indicates that the vinyl pyrrolidone-vinyl acetate copolymer plays an important role in dispersing the nano inorganic powder in the modification process, and the dispersing uniformity of the nano inorganic powder in the high-tensile-strength impact modifier is affected without adding the dispersing agent, so that the reinforcing and toughening effects of the high-tensile-strength impact modifier on the polyvinyl chloride are affected; in comparative example 3, in which hyperbranched polyglycidyl and amino-terminated hyperbranched polyamide are not added, the reduction of the bending strength, the elongation at break and the notched impact strength is very large, and the tensile strength and the Vicat softening point are also very obviously reduced, which shows that the hyperbranched polyglycidyl and amino-terminated hyperbranched polyamide can enhance the toughness of polyvinyl chloride, and simultaneously have very obvious improvement effect on the tensile strength and the heat resistance; comparative example 4, in which no hydroxyl-terminated polybutadiene was added, the decrease in flexural strength and elongation at break was very severe, indicating that the hydroxyl-terminated polybutadiene had a remarkable effect on improving the toughness of polyvinyl chloride.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (4)
1. A high tensile strength impact modifier for polyvinyl chloride, characterized in that:
the high-tensile-strength impact modifier for polyvinyl chloride is viscous liquid, and mainly comprises lignin coated by nitrile rubber, modified nano inorganic powder, hyperbranched polyglycidyl, amino-terminated hyperbranched polyamide and hydroxyl-terminated polybutadiene;
the mass ratio of the nitrile rubber coated lignin to the modified nano inorganic powder to the hyperbranched polyglycidyl to the amino-terminated hyperbranched polyamide to the hydroxyl-terminated polybutadiene is 10-25:15-40:5-13:10-20:25-35;
the molecular weight of the hyperbranched polyglycidyl is 800-2500 g/mol;
The amino-terminated hyperbranched polyamide has the amino-terminated number of 4-14 mol/mol, the molecular weight of 300-1400 g/mol and the property of yellow liquid;
the hydroxyl value of the hydroxyl-terminated polybutadiene is 50-110 mg KOH/g, the viscosity at 40 ℃ is 1-20 Pa-s, and the molecular weight is 900-4000 g/mol;
The preparation method of the nitrile rubber coated lignin comprises the following steps: drying lignin at 90-110 ℃ for 20-30 hours, putting the lignin into a planetary ball mill thoroughly drying and dewatering, adding toluene with the mass of 20-40 wt% of the lignin, controlling the rotating speed to 1500-2200 r/min, grinding to the particle size of 0.01-0.9 mu m, putting the ground lignin slurry into a dry and anhydrous reaction kettle, adding toluene with the mass of 0.8-1.1 times of the lignin slurry, controlling the stirring speed to 3000-6000 r/min, heating and keeping the temperature to 80-95 ℃, slowly dripping isocyanate, continuing to stir at the constant temperature for 6-10 hours after dripping, adding carboxyl-terminated nitrile rubber, continuing to stir and reacting until the mass content of liquid isocyanate groups in the kettle is 0wt%, stopping stirring and cooling to room temperature, centrifuging, and vacuum drying separated solid at 50-80 ℃ for 8-14 hours to obtain nitrile rubber coated lignin;
The preparation method of the modified nano inorganic powder comprises the following steps: drying nano calcium carbonate and gas-phase silicon dioxide at a high temperature of 100-140 ℃ for 15-22 hours, then placing the nano calcium carbonate and gas-phase silicon dioxide into a high-speed dispersion kettle, adding absolute ethyl alcohol and vinyl pyrrolidone-vinyl acetate copolymer, controlling the dispersion rate to be 6000-9500 r/min, heating and keeping the temperature to 50-70 ℃ for 5-9 hours, adding 3-diethylenetriamine propyl trimethoxy silane, reducing the dispersion rate to 3500-4500 r/min, keeping the temperature for 8-14 hours, cooling to room temperature, centrifuging, and vacuum drying the obtained solid at 50-70 ℃ for 4-7 hours to obtain the modified nano inorganic powder.
2. The high tensile strength impact modifier for polyvinyl chloride according to claim 1, wherein:
slowly dropwise adding isocyanate, wherein the adding mass of the isocyanate is 10-35 wt% of the mass of lignin, and the dropping speed is 10-60 g/min;
The isocyanate is one of toluene diisocyanate and diphenylmethane diisocyanate;
The addition amount of the carboxyl-terminated nitrile rubber is 8-20wt% of the lignin;
the carboxyl content of the carboxyl-terminated nitrile rubber is 0.5-0.7 mol/kg, the viscosity at 40 ℃ is 6-11 Pa.s, and the number average molecular weight is 2000-4000 g/mol.
3. The high tensile strength impact modifier for polyvinyl chloride according to claim 1, wherein:
The particle size of the nano calcium carbonate is 5-30 nm;
The particle size of the fumed silica is 10-50 nm;
the model of the vinyl pyrrolidone-vinyl acetate copolymer is VA64, and the K value is 26-33;
The material adding mass ratio of the nano calcium carbonate to the fumed silica to the absolute ethyl alcohol to the vinyl pyrrolidone-vinyl acetate copolymer to the 3-diethylenetriamine propyl trimethoxy silane is 10-35:5-20:130-180:0.5-1.2:2-7.
4. The method for preparing a high tensile strength impact modifier for polyvinyl chloride according to claim 1, wherein:
According to the mass ratio of the nitrile rubber coated lignin, the modified nano inorganic powder, the hyperbranched polyglycidyl, the amino-terminated hyperbranched polyamide and the hydroxyl-terminated polybutadiene are initially mixed and then are placed on a high-speed dispersing machine to be dispersed for 16-20 hours at 25000-35000 rpm, then the nitrile rubber coated lignin is added, the dispersion is continued for 10-14 hours, and then the discharged material is obtained, so that the obtained viscous liquid is the high-tensile-strength impact modifier.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232139A2 (en) * | 1986-01-30 | 1987-08-12 | The Dow Chemical Company | Impact modifiers for polyvinyl chloride resins |
| DE4408855A1 (en) * | 1994-03-16 | 1995-09-21 | Rawema Industrieanlagen Gmbh | Solid or foamed plastic using biomass as filler |
| CN107540975A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of high rush-resistant polyvinyl chloride water-feeding pipes and preparation method thereof |
| CN108659263A (en) * | 2018-05-24 | 2018-10-16 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of modified calcium carbonate and its application in PVC wood plastic clad plate |
| CN109135106A (en) * | 2018-07-23 | 2019-01-04 | 爱康企业集团(上海)有限公司 | A kind of environment-friendly anti-aging toughening hard PVC transparent pipe and preparation method thereof |
| CN113402675A (en) * | 2021-08-23 | 2021-09-17 | 山东昌泰高分子材料股份有限公司 | Preparation method of acrylate impact modifier |
-
2024
- 2024-04-16 CN CN202410451447.4A patent/CN118048043B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232139A2 (en) * | 1986-01-30 | 1987-08-12 | The Dow Chemical Company | Impact modifiers for polyvinyl chloride resins |
| DE4408855A1 (en) * | 1994-03-16 | 1995-09-21 | Rawema Industrieanlagen Gmbh | Solid or foamed plastic using biomass as filler |
| CN107540975A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of high rush-resistant polyvinyl chloride water-feeding pipes and preparation method thereof |
| CN108659263A (en) * | 2018-05-24 | 2018-10-16 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of modified calcium carbonate and its application in PVC wood plastic clad plate |
| CN109135106A (en) * | 2018-07-23 | 2019-01-04 | 爱康企业集团(上海)有限公司 | A kind of environment-friendly anti-aging toughening hard PVC transparent pipe and preparation method thereof |
| CN113402675A (en) * | 2021-08-23 | 2021-09-17 | 山东昌泰高分子材料股份有限公司 | Preparation method of acrylate impact modifier |
Non-Patent Citations (3)
| Title |
|---|
| 刘海: ""耐热抗冲PVC复合材料的制备、结构与性能"", 《中国博士学位论文全文数据库工程科技Ⅰ辑》, no. 4, 15 April 2013 (2013-04-15), pages 016 - 5 * |
| 岳小鹏: ""木质素在PVC复合材料中的应用研究"", 《中国博士学位论文全文数据库工程科技Ⅰ辑》, 15 December 2011 (2011-12-15), pages 020 - 12 * |
| 张建民，等: ""不饱和超支化聚(酰胺-酯)改性PVC 研究"", 《化工新型材料》, vol. 33, no. 12, 31 December 2005 (2005-12-31), pages 84 - 86 * |
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