CN109627675A - A kind of enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy and preparation method thereof - Google Patents
A kind of enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy and preparation method thereof Download PDFInfo
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- CN109627675A CN109627675A CN201811596265.7A CN201811596265A CN109627675A CN 109627675 A CN109627675 A CN 109627675A CN 201811596265 A CN201811596265 A CN 201811596265A CN 109627675 A CN109627675 A CN 109627675A
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- Prior art keywords
- mixed
- acrylonitrile copolymer
- screw extruder
- minutes
- modified lignin
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- 229920005610 lignin Polymers 0.000 title claims abstract description 60
- 229920001577 copolymer Polymers 0.000 title claims abstract description 42
- 239000000956 alloy Substances 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 28
- 239000011347 resin Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 7
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- -1 polyethylene Polymers 0.000 claims description 14
- 239000008188 pellet Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- 238000006884 silylation reaction Methods 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 claims 1
- 229920001732 Lignosulfonate Polymers 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 3
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- XOTCJLJXDBVZBQ-UHFFFAOYSA-N CO[SiH](OC)OC.CCCOC(=O)C(C)=C Chemical compound CO[SiH](OC)OC.CCCOC(=O)C(C)=C XOTCJLJXDBVZBQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical group Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
A kind of enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy, the component including following mass fraction: 100 parts of PVC, 50-250 parts of acrylonitrile copolymers, 10-150 parts of modified lignin resins, 2-15 parts of heat stabilizers, 0.1-8 parts of lubricants, 1-20 parts of anti-impact modifiers.The invention also discloses the preparation methods of above-mentioned alloy.The enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy prepared by the present invention can be improved acrylonitrile copolymer/PVC alloy mechanical property, and improve anti-ultraviolet aging, antioxidative effect, environmentally protective, reduce cost.
Description
Technical field
Present invention relates in general to polymer blend compositions, belong to high molecular material field of compounding, and in particular to a kind of
The enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy and preparation method thereof.
Background technique
Acrylonitrile copolymer/PVC alloy is total to acrylonitrile copolymer and the acrylonitrile that the PVC with anti-flammability is prepared into
Polymers/PVC alloy, with excellent fire-retardant and mechanical property, can be widely used in household electrical appliance, electronics, aeronautical instrument,
The every field such as automobile, train, building materials.Number of patent application 201010269113.3 discloses a kind of PVC/ of high impact strength
ABS alloy composite material and its preparation method add active nano-calcium carbonate to reduce cost and improve the bending die of alloy material
Amount acts synergistically with CPE, improves the impact property of alloy material, and do not influence on mobile phase, but in the invention, do not have
Correlative study is carried out to the uvioresistant effect of PVC/ABS alloy and heat stabilization.License publication number CN 103351573
B has invented a kind of anti-aging resistant ABS-PVC plastic alloy, and the heat aging performance of alloy is improved using age resister, improves material
Use temperature range.
Lignin is to be gathered by phenylpropyl alcohol alkyl structure unit by the netted amorphous height that ehter bond, ester bond are connected with carbon-carbon bond
Object is widely present in the cell wall of plant fiber.Itself has certain bonding force, can be used as adhesive use, in addition,
Compared with cellulose and hemicellulose, lignin shows weaker hydrophily, relatively good with the compatibility of polymeric matrix.Cause
This, can improve wood plastics composite for lignin as coupling agent using the bonding force of lignin and with the compatibility of polymeric matrix
The interface binding power of material increases mechanical strength.Application number 201611050067.1 disclose a kind of flame-retardant ABS compound material and
Preparation method uses melamine and phosphorus pentoxide to be modified lignin, then preparation high flame retardant is compounded with ABS
The composite material of energy.But for lignin be applied to the research of acrylonitrile copolymer/PVC alloy do not have, this patent be by
Lignin is applied in acrylonitrile copolymer/PVC alloy, can not only improve the mechanical property and antioxygenic property of alloy,
The dosage that lignin can be improved, turns waste into wealth, conservation of nature.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of enhanced acrylonitrile copolymer of modified lignin resin/PVC to close
Gold is not fully utilized the problems such as bad with alloy property with solving lignin of the existing technology.
The present invention also technical problems to be solved are to provide the enhanced acrylonitrile copolymer of above-mentioned modified lignin resin/PVC and close
The preparation method of gold.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy, the component including following mass fraction:
The above-mentioned enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy, preferably includes the component of following mass fraction:
The above-mentioned enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy most preferably includes the group of following mass fraction
Point:
Wherein, the acrylonitrile copolymer is the copolymer of acrylonitrile monemer and vinyl compound, and acrylonitrile list
The content of body is at least 20wt%.The acrylonitrile copolymer be preferably styrene-acrylonitrile-butadiene copolymer (ABS),
Styrene-acrylonitrile copolymer (SAN), acrylonitrile-styrene-acrylic rubber copolymer (ASA).
Wherein, the lignin is enzymolysis xylogen, black liquid lignin by acid separation, sulfate-reducing conditions, lignin
Any one or the combination of several of them of sulfonate, alkali lignin or organic solvent lignin.
Wherein, the modified lignin resin is to be carried out in chlorination or the modified lignin of silylation based on lignin
Any one or the combination of several of them.Wherein, it is described it is chlorination modified for by gas phase, organic solvent method, Aqueous phase to lignin
Chlorination is carried out, wherein preferable organic solvent method and Aqueous phase.It is described it is silane-modified for by silane coupling agent to lignin into
Row graft modification.Wherein, the silane coupling agent is vinyl trichlorosilane, vinyltriethoxysilane, vinyl three
Methoxy silane, vinyl three (beta-methoxy ethyoxyl) silane, γ-propyl methacrylate trimethoxy silane, 3- aminopropyl
Triethoxysilane, 3- TSL 8330, wherein preferred vinyl triethoxysilane and vinyl trimethoxy
Base silane.
Wherein, the heat stabilizer is in complex lead salt stabilizer, Environment-friendlycalcium calcium zinc stabilizer and organic tin stabilizer
Any one or the combination of several of them.
Wherein, the lubricant is any one or the combination of several of them in polyethylene wax, stearic acid and polyol ester.
Wherein, the anti-impact modifier be haloflex CPE, it is ethylene-vinyl acetate copolymer EVA, high-elastic
Any one or a few group in property acrylic ester modifier ACR, glycidyl methacrylate GMA and EP rubbers
It closes.
The preparation method of the above-mentioned enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy, including following five kinds of sides of preparation
Method optionally one of:
Method 1: each group of formula ratio is placed in mixing machine and is mixed, is granulated using parallel double-screw extruder, then is passed through
Conical double screw extruder carries out squeezing out pressing plate to obtain the final product；
Method 2: each component of formula ratio is mixed, and first through mixer mixing, then through vulcanizing press hot pressing and cold pressing is
?；
Method 3: each component of formula ratio is mixed, is using open mill mill, then through vulcanizing press hot pressing and cold pressing
?；
Method 4: each group of formula ratio is placed in mixing machine and is mixed, then is squeezed out through conical double screw extruder to obtain the final product；
Method 5: each group of formula ratio is placed in mixing machine and is mixed, then is granulated through parallel double-screw extruder, then
It is molded through injection molding machine to obtain the final product.
In method 1, each group of formula ratio is placed in mixing machine under the conditions of 110-130 DEG C and is mixed 5-15 minutes, then
Cold 5-15 minutes mixed at 50-90 DEG C, mixing revolving speed maintains 200-550rpm, obtains just mixed material；First mixed material is added
Enter to squeeze out in parallel double-screw extruder and be blended, is cut into pellet, the work of parallel double-screw extruder using plastic grain cutting machine
Temperature is 170-200 DEG C, revolving speed 200-400rpm；Prepared pellet is added in conical double screw extruder and is squeezed
Pressing plate out, the operating temperature of conical double screw extruder are 170-200 DEG C, revolving speed 200-400rpm.
In method 2, each component mixing is weighed according to formula ratio, in mixer mixing 5-10 points under the conditions of 170-200 DEG C
Clock；Use vulcanizing press hot pressing 3-6 minutes under the conditions of 170-200 DEG C again, then 15-28 DEG C cold pressing 2-5 minutes.
In method 3, each component mixing, using open mill mill 5-10 minutes, wherein preliminary roller 130- are weighed according to formula ratio
170 DEG C, 170-200 DEG C of back roller；Again through vulcanizing press hot pressing 3-6 minutes under the conditions of 170-200 DEG C, then 15-28 DEG C it is cold
Pressure 2-5 minutes.
In method 4, each group weighed according to formula ratio be placed in mixing machine under the conditions of 110-130 DEG C and mix 5-15 minutes,
Cold 5-15 minutes mixed under the conditions of 50-90 DEG C again, mixing revolving speed maintains 200-550rpm, obtains just mixed material；It will just mix
It closes material to be added in conical double screw extruder, under the conditions of 170-200 DEG C, revolving speed 200-400rpm prepares composite wood
Material.
In method 5, each group weighed according to formula ratio be placed in mixing machine under the conditions of 110-130 DEG C and mix 5-15 minutes,
Cold 5-15 minutes mixed under the conditions of 50-90 DEG C again, mixing revolving speed maintains 200-550rpm, obtains just mixed material；It will just mix
It closes material and is added to extrusion blending in parallel double-screw extruder, be cut into pellet, double screw extruder using plastic grain cutting machine
Operating temperature be 170-200 DEG C, revolving speed 200-400rpm；Then by prepared pellet as in injection molding machine, in 190-
Composite material is prepared under the conditions of 220 DEG C.
In above-mentioned five kinds of methods, most preferred method 1.
The utility model has the advantages that compared with prior art, the present invention has the advantage that
The invention proposes for prepare high-performance acrylonitrile copolymer/new method of PVC alloy.By being carried out to lignin
Modified, chlorination, silylation improve the compatibility of itself and PVC and acrylonitrile copolymer, improve the whole mechanics of alloy
Performance.In addition, absorbing functional group, such as aromatic radical, conjugated double bond containing a large amount of uvioresistant in lignin, alloy can be improved
Uvioresistant, inoxidizability and other effects.Therefore, the present invention can not only improve lignin dosage, protect environment, can also improve propylene
Lonitrile copolymer/PVC alloy mechanical property and uvioresistant, antioxidative effect.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
Embodiment 1:
Raw material (parts by weight): 100 parts of PVC, 200 parts of styrene-acrylonitrile-butadiene copolymer ABS, 80 parts of chlorinations are wooden
Element, 8 parts of calcium zinc stabilizers, 0.2 part of stearic acid, 0.2 part of polyethylene wax, 15 parts of haloflex CPE, 2 parts of methacrylic acid contractings
Water glyceride.
Manufacturing method includes the following steps:
(1) all raw materials are placed in mixing machine and are mixed 10 minutes for 130 DEG C, then cold 10 minutes mixed, the mixing turn at 50 DEG C
Speed maintains 200-550rpm, obtains just mixed material；
(2) first mixed material is added to squeeze out in double screw extruder and is blended, be cut into pellet using plastic grain cutting machine,
The operating temperature of double screw extruder is 190 DEG C, revolving speed 210rpm；
(3) prepared pellet is added in the double extruders of cone and carries out extrusion pressing plate, boring double extruder operating temperatures is
185 DEG C, revolving speed be 200rpm to get.
Embodiment 2:
Raw material (parts by weight): 100 parts of PVC, 150 parts of styrene-acrylonitrile copolymer SAN, 70 parts of silylation lignin,
7 parts of complex lead salt stabilizers, 0.3 part of polyol ester, 0.1 part of polyethylene wax, 10 parts of ethylene-vinyl acetate copolymer EVA.
Manufacturing method includes the following steps:
(1) according to formula ratio weigh certain PVC, acrylonitrile copolymer, modified lignin resin, heat stabilizer, lubricant and
Anti-impact modifier；
(2) material is mixed 10 minutes as 110 DEG C in mixing machine, then cold 10 minutes mixed, the mixing revolving speed dimension at 50 DEG C
It holds in 200-550rpm, obtains just mixed material；
(3) material is added in the double extruders of cone, at 190 DEG C, revolving speed 250rpm prepares composite material.
Embodiment 3:
Raw material (parts by weight): 100 parts of PVC, 150 parts of acrylonitrile-styrenes-acrylic rubber copolymer (ASA), 90 parts of chlorine
Change lignin, 8 parts of calcium zinc stabilizers, 0.2 part of stearic acid, 0.2 part of polyethylene wax, 15 parts of tenacity acrylic's esters modification agent
ACR。
Manufacturing method includes the following steps:
(1) according to formula ratio weigh certain PVC, acrylonitrile copolymer, modified lignin resin, heat stabilizer, lubricant and
Anti-impact modifier；
(2) material is mixed 10 minutes as 110 DEG C in mixing machine, then cold 10 minutes mixed, the mixing revolving speed dimension at 55 DEG C
It holds in 200-550rpm, obtains just mixed material；
(3) first mixed material is added to squeeze out in double screw extruder and is blended, be cut into pellet using plastic grain cutting machine,
The operating temperature of double screw extruder is 180 DEG C, revolving speed 250rpm；
(4) prepared pellet at 200 DEG C, is prepared into composite material as in injection molding machine.
Embodiment 4:
Raw material (parts by weight): 100 parts of PVC, 100 parts of styrene-acrylonitrile copolymer SAN, 60 parts of silylation lignin,
6 parts of organic tin stabilizers, 0.1 part of stearic acid, 0.3 part of polyol ester, 10 parts of third glue of second rubber.
Manufacturing method includes the following steps:
(1) according to formula ratio weigh certain PVC, acrylonitrile copolymer, modified lignin resin, heat stabilizer, lubricant and
Anti-impact modifier；
(2) 170 DEG C of preliminary roller, 185 DEG C of back roller, open mill mill 7 minutes；
(3) vulcanizing press is used, then hot pressing 4 minutes at 175 DEG C are cold-pressed 3 minutes for 28 DEG C.
Embodiment 5:
Raw material (parts by weight): 100 parts of PVC, 120 parts of styrene-acrylonitrile-butadiene copolymer ABS, 60 parts of chlorinationization wood
Quality, 6 parts of organic tin stabilizers, 0.1 part of stearic acid, 0.3 part of polyol ester, 10 parts of haloflex CPE.
Manufacturing method includes the following steps:
(1) according to formula ratio weigh certain PVC, acrylonitrile copolymer, modified lignin resin, heat stabilizer, lubricant and
Anti-impact modifier；
(2) at 190 DEG C, mixing 6 minutes；
(3) vulcanizing press is used, then hot pressing 4 minutes at 175 DEG C are cold-pressed 3 minutes for 28 DEG C.
Comparative example 1:
Raw material (parts by weight): 100 parts of PVC, 200 parts of styrene-acrylonitrile-butadiene copolymer ABS, 8 parts of organotins are steady
Determine agent, 0.2 part of stearic acid, 0.2 part of polyethylene wax, 15 parts of chlorination second third glue of rubber.
Manufacturing method is the same as embodiment 1.
Comparative example 2:
Raw material (parts by weight): 100 parts of PVC, 200 parts of styrene-acrylonitrile-butadiene copolymer ABS, 80 parts of lignin, 8
Part complex lead salt stabilizer, 0.2 part of stearic acid, 0.2 part of polyethylene wax, 15 parts of haloflex CPE.
Manufacturing method is the same as embodiment 1.
Grinding process is carried out to the surface of above-mentioned composite material section bar product, performance detection, testing result are carried out to product
As shown in table 1.
Detection method is as follows:
Notch impact strength: GB/T 1843-2008
Tensile strength, tension fracture elongation rate, tensile modulus of elasticity: GB/T 1040.2-2006
Bending strength, bending modulus: GB/T 9341-2008
Anti-ultraviolet ageing~bending strength retention rate: GB/T24508-2009 " Wood-plastic floor "
Ageing properties~fracture load by bending retention rate: GB/T16422.3-2014
Table 1
Experiment shows that, compared to pure ABS/PVC alloy, after adding modified lignin resin, the toughness of alloy (stretch by tension failure
Long rate, notch impact strength) decline, but it is higher than unmodified lignin, and after adding modified lignin resin, the stretching of alloy
Intensity and bending strength increase, and anti-aging property is significantly improved.
Claims (13)
1. a kind of enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy, which is characterized in that including following mass fraction
Component:
2. the enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy according to claim 1, which is characterized in that described
Acrylonitrile copolymer be acrylonitrile monemer and vinyl compound copolymer, and the content of acrylonitrile monemer is at least
20wt%.
3. the enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy according to claim 1, which is characterized in that described
Lignin be enzymolysis xylogen, black liquid lignin by acid separation, sulfate-reducing conditions, lignosulfonates, alkali lignin or
Any one or the combination of several of them of organic solvent lignin.
4. the enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy according to claim 1, which is characterized in that described
Modified lignin resin be that any one or a few in chlorination or the modified lignin of silylation is carried out based on lignin
Combination.
5. the enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy according to claim 1, which is characterized in that described
Heat stabilizer be complex lead salt stabilizer, calcium zinc stabilizer and organic tin stabilizer in any one or a few group
It closes.
6. the enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy according to claim 1, which is characterized in that described
Lubricant be polyethylene wax, stearic acid, polyol ester and compounded lubricant in any one or the combination of several of them.
7. the enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy according to claim 1, which is characterized in that described
Anti-impact modifier be haloflex, ethylene-vinyl acetate copolymer, the agent of tenacity acrylic's esters modification, methyl
Any one or the combination of several of them in glycidyl acrylate and EP rubbers.
8. the preparation side of the enhanced acrylonitrile copolymer of modified lignin resin/PVC alloy according to any one of claims 1 to 7
One of method, which is characterized in that optionally including following five kinds of preparation methods:
Method 1: each group of formula ratio is placed in mixing machine and is mixed, is granulated using parallel double-screw extruder, then through taper
Double screw extruder carries out squeezing out pressing plate to obtain the final product；
Method 2: each component of formula ratio is mixed, first through mixer mixing, then through vulcanizing press hot pressing and is cold-pressed to obtain the final product；
Method 3: each component of formula ratio is mixed, using open mill mill, then through vulcanizing press hot pressing and is cold-pressed to obtain the final product；
Method 4: each group of formula ratio is placed in mixing machine and is mixed, then is squeezed out through conical double screw extruder to obtain the final product；
Method 5: each group of formula ratio is placed in mixing machine and is mixed, then is granulated through parallel double-screw extruder, then through infusing
Molding machine is molded to obtain the final product.
9. preparation method according to claim 8, which is characterized in that in method 1, each group of formula ratio is placed in mixing
Mixed 5-15 minutes under the conditions of 110-130 DEG C in machine, then at 50-90 DEG C it is cold 5-15 minutes mixed, mixing revolving speed maintain 200-
550rpm obtains just mixed material；First mixed material is added to squeeze out in parallel double-screw extruder and is blended, is cut using plastics
Grain machine-cut is 170-200 DEG C at pellet, the operating temperature of parallel double-screw extruder, revolving speed 200-400rpm；It will be prepared
Pellet be added in conical double screw extruder and carry out extrusion pressing plate, the operating temperature of conical double screw extruder is 170-
200 DEG C, revolving speed 200-400rpm.
10. preparation method according to claim 8, which is characterized in that in method 2, it is mixed to weigh each component according to formula ratio
It closes, in mixer mixing 5-10 minutes under the conditions of 170-200 DEG C；It is hot under the conditions of 170-200 DEG C using vulcanizing press again
Pressure 3-6 minutes, then 15-28 DEG C cold pressing 2-5 minutes.
11. preparation method according to claim 8, which is characterized in that in method 3, it is mixed to weigh each component according to formula ratio
It closes, using open mill mill 5-10 minutes, wherein 130-170 DEG C of preliminary roller, 170-200 DEG C of back roller；Again through vulcanizing press in
Hot pressing 3-6 minutes under the conditions of 170-200 DEG C, then 15-28 DEG C cold pressing 2-5 minutes.
12. preparation method according to claim 8, which is characterized in that in method 4, weigh each group according to formula ratio and split
It is mixed 5-15 minutes under the conditions of 110-130 DEG C in mixing machine, then cold 5-15 minutes mixed, mixing revolving speed under the conditions of 50-90 DEG C
200-550rpm is maintained, just mixed material is obtained；First mixed material is added in conical double screw extruder, in 170-
Under the conditions of 200 DEG C, revolving speed 200-400rpm prepares composite material.
13. preparation method according to claim 8, which is characterized in that in method 5, weigh each group according to formula ratio and split
It is mixed 5-15 minutes under the conditions of 110-130 DEG C in mixing machine, then cold 5-15 minutes mixed, mixing revolving speed under the conditions of 50-90 DEG C
200-550rpm is maintained, just mixed material is obtained；First mixed material is added to squeeze out in parallel double-screw extruder and is blended,
It is cut into pellet using plastic grain cutting machine, the operating temperature of double screw extruder is 170-200 DEG C, revolving speed 200-400rpm；
Then prepared pellet is prepared into composite material under the conditions of 190-220 DEG C as in injection molding machine.
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