CN116675936A - Wear-resistant plastic with ageing resistance - Google Patents
Wear-resistant plastic with ageing resistance Download PDFInfo
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- CN116675936A CN116675936A CN202310738330.XA CN202310738330A CN116675936A CN 116675936 A CN116675936 A CN 116675936A CN 202310738330 A CN202310738330 A CN 202310738330A CN 116675936 A CN116675936 A CN 116675936A
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- wear
- polyvinyl chloride
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- stirring
- resistant
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- 229920003023 plastic Polymers 0.000 title claims abstract description 70
- 239000004033 plastic Substances 0.000 title claims abstract description 70
- 230000032683 aging Effects 0.000 title claims abstract description 30
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 86
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 86
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 240000008564 Boehmeria nivea Species 0.000 claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 23
- 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 claims abstract description 21
- 239000003063 flame retardant Substances 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 51
- 239000002585 base Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 16
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 16
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 16
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 16
- -1 polyethylene Polymers 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 239000001993 wax Substances 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011343 solid material Substances 0.000 claims description 12
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000005299 abrasion Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 claims description 8
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- XUJNEKJLAYXESH-UHFFFAOYSA-N Cysteine Chemical compound SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229940078469 dl- cysteine Drugs 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- 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
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to the technical field of plastics and discloses wear-resistant plastics with ageing resistance, which are prepared by taking a polyvinyl chloride base material as a base material, taking a wear-resistant auxiliary agent, a plasticizer, a lubricant, a stabilizer and a flame retardant as auxiliary materials and carrying out blending and extrusion granulation, wherein hindered phenol groups are introduced into a polyvinyl chloride structure, and polyvinyl chloride molecular chains are made to be in a cross-linked structure in the process of introduction to form the polyvinyl chloride base material, so that the prepared polyvinyl chloride plastic structure is more compact, meanwhile, a nano calcium carbonate-ramie fiber compound is prepared, and the nano calcium carbonate can form a special ball structure by utilizing the characteristics of high strength and high toughness of ramie fibers after being mixed with the polyvinyl chloride base material as the wear-resistant auxiliary agent, so that the prepared polyvinyl chloride plastic has excellent comprehensive performances such as wear resistance, heat resistance and ageing resistance.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to wear-resistant plastics with ageing resistance.
Background
In recent years, plastics are increasingly used in life, wherein polyvinyl chloride is one of the general plastics with the largest output in the world, has relatively stable physical properties, good electrical insulation and strong corrosion resistance, and is widely used in the field of common daily necessities such as building materials, floor leathers, floor tiles, artificial leathers, pipes, wires and cables, packaging materials, sealing materials, fibers and the like, but the heat resistance, ageing resistance, wear resistance and the like of the polyvinyl chloride are poor, and the polyvinyl chloride used in the special fields such as wires and cables is ageing and worn, so that lines are exposed and potential safety hazards are easily caused, and therefore, in practical application, the polyvinyl chloride is often required to be improved in ageing resistance, wear resistance and the like.
At present, the most common modification means of polyvinyl chloride is to add fillers with various functionalities in the process of preparing polyvinyl chloride plastics for blending modification, for example, the invention patent with the application number of CN201410076165.7 discloses a technology related to a polyethylene material, and the technology is to mix the polyvinyl chloride material with a polyvinyl chloride base material by using nitrile rubber powder as a filling modifier, so that the prepared polyvinyl chloride material has good comprehensive properties of wear resistance, thermal stability, weather resistance, mechanics and the like, but the simple mixing of the polyvinyl chloride base material and assistants such as nitrile rubber is difficult to eliminate the interface repulsive effect between the polyvinyl chloride base material and the nitrile rubber, and the unavoidable phenomenon of phase separation occurs in the long-term use process, so that the mechanical property of the polyvinyl chloride material is greatly reduced.
Based on the above, the invention provides a wear-resistant plastic with ageing resistance, which can solve the technical problems.
Disclosure of Invention
The invention aims to provide wear-resistant plastic with ageing resistance, and aims to solve the problems of poor wear resistance, heat resistance and ageing resistance of polyvinyl chloride by starting from a polyvinyl chloride structure, preparing a polyvinyl chloride base material with a cross-linked structure and adding nano calcium carbonate and ramie fiber composite wear-resistant auxiliary agent.
The aim of the invention can be achieved by the following technical scheme:
the wear-resistant plastic with the ageing resistance comprises the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride base stock, 2-5 parts of wear-resistant auxiliary agent, 5-10 parts of plasticizer, 4-8 parts of lubricant, 1-2 parts of stabilizer and 2-6 parts of flame retardant;
the polyvinyl chloride base material is polyvinyl chloride grafted with hindered phenol groups in the structure;
the wear-resistant auxiliary agent is a compound of nano calcium carbonate and ramie fibers.
Further, the plasticizer is any one of dioctyl phthalate, trioctyl trimellitate or tributyl citrate; the lubricant is any one of stearic acid, paraffin wax or polyethylene wax; the stabilizer is a liquid calcium-zinc stabilizer; the flame retardant is ammonium polyphosphate.
Further, the preparation method of the polyvinyl chloride base material comprises the following steps:
step (1): mixing polyvinyl chloride powder with chloroform, stirring uniformly, adding DL-cysteine and an acid binding agent, stirring uniformly, introducing nitrogen to remove oxygen, stirring at 55-60 ℃ for 12-24 hours, cooling the materials, pouring the materials into methanol for precipitation, filtering and separating solid materials, washing, and drying in vacuum to obtain an intermediate material;
step (2): mixing the intermediate material with ethanol, stirring uniformly, adding 3, 5-di-tert-butyl-4-hydroxybenzyl alcohol and a composite catalyst into the system, stirring at room temperature for 12-18h under the protection of nitrogen, pouring the material into methanol for precipitation, separating out solid materials, washing, and drying in vacuum to obtain the polyvinyl chloride base material.
Further, in the step (1), the acid binding agent is any one of sodium carbonate and potassium carbonate.
Further, in the step (2), the composite catalyst is a 4-dimethylaminopyridine and dicyclohexylcarbodiimide composite, and the mass ratio of the 4-dimethylaminopyridine to the dicyclohexylcarbodiimide is 0.2-0.35:1.
According to the technical scheme, the polyvinyl chloride structure contains halogen chlorine atoms, nucleophilic substitution reaction can be carried out on the halogen chlorine atoms and amino and mercapto groups in the DL-cysteine structure under the action of an acid-binding agent sodium carbonate or potassium carbonate, active carboxyl groups are contained in the structure, and the polyvinyl chloride intermediate material with a crosslinking structure is formed, and under the action of a composite catalyst of 4-dimethylaminopyridine and dicyclohexylcarbodiimide, the active carboxyl groups in the structure can further carry out esterification reaction with benzyl alcohol groups in the 3, 5-di-tert-butyl-4-hydroxy benzyl alcohol structure, so that hindered phenol groups are grafted into the polyvinyl chloride structure, and the polyvinyl chloride base stock is prepared.
Further, the preparation method of the wear-resistant auxiliary agent comprises the following steps:
step (1): adding nano calcium carbonate into toluene, uniformly dispersing by ultrasonic, adding 3-isocyanatopropyl triethoxysilane, stirring uniformly, stirring at room temperature for 6-12h, centrifuging to separate a solid product, and drying in vacuum to obtain isocyanated nano calcium carbonate;
step (2): mixing isocyanated nano calcium carbonate with absolute ethyl alcohol, uniformly dispersing by ultrasonic, adding alkali-treated ramie fibers and dibutyl tin dilaurate, continuing to stand for 20-30min, raising the system temperature to 60-70 ℃, stirring at constant temperature for 12-24h, centrifugally separating solid materials, washing, and drying in vacuum to obtain the wear-resistant auxiliary agent.
Further, in the step (1), the particle size of the nano calcium carbonate is less than or equal to 100nm.
According to the technical scheme, the surface of the nano calcium carbonate contains a large number of hydroxyl groups, after the nano calcium carbonate is modified by 3-isocyanatopropyl triethoxysilane, a large number of isocyanate groups are generated on the surface of the nano calcium carbonate, the surface of the ramie fiber subjected to alkali treatment can generate a large number of active hydroxyl groups, and the active hydroxyl groups can react with the isocyanate groups in the isocyanated nano calcium carbonate under the catalysis of dibutyltin dilaurate, so that the nano calcium carbonate and the ramie fiber are organically combined under the condition of continuous stirring, and the wear-resistant auxiliary agent is prepared.
Further, in the step (2), the preparation method of the alkali treated ramie fiber specifically comprises the following steps: soaking ramie fiber in 5-15% sodium hydroxide solution for 20-30 hr, filtering to separate solid material, washing with purified water to neutrality, and vacuum drying.
Further, the length of the ramie fibers is 1-2mm, and the average diameter is 50um.
Further, the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride base stock, wear-resistant auxiliary agent, lubricant, stabilizer and flame retardant in parts by weight into a stirring kettle, and stirring for 30-60min at a stirring rate of 500-1000r/min to form premix;
step two: adding the plasticizer into the premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each area of the extruder to be 100-140 ℃ and the screw rotation speed to be 20-30r/min, and carrying out extrusion granulation to obtain the wear-resistant plastic.
The invention has the beneficial effects that:
(1) According to the invention, the hindered phenol group is introduced into the polyvinyl chloride structure, and in the process of introduction, the polyvinyl chloride molecular chain is in a cross-linked structure to form the polyvinyl chloride base material, the existence of the hindered phenol group can react with free radicals generated in the ageing process of the polyvinyl chloride to interrupt the growth of an active chain, so that the ageing resistance of the polyvinyl chloride is effectively improved, the hindered phenol group is connected into the polyvinyl chloride base body in a chemical bond mode, the interface incompatibility problem between two phases does not exist, and phase separation does not occur even if the polyvinyl chloride plastic is used for a long time, so that the prepared polyvinyl chloride plastic has a long-acting ageing resistance effect. In addition, the density of the polyvinyl chloride molecular chains of the cross-linked structure is higher, so that the prepared polyvinyl chloride plastic structure is more compact, and further higher heat resistance and mechanical strength are realized.
(2) According to the invention, the nano calcium carbonate-ramie fiber composite wear-resistant auxiliary agent is prepared, and as the nano calcium carbonate surface still contains unreacted isocyanate groups, the nano calcium carbonate still can interact with active functional groups such as imino groups in a polyvinyl chloride base material structure in the subsequent high-temperature extrusion process, so that the interface compatibility of the wear-resistant auxiliary agent and the polyvinyl chloride base material is improved, the wear-resistant auxiliary agent is uniformly dispersed in the polyvinyl chloride base material structure, a polyvinyl chloride cross-linked network taking the wear-resistant auxiliary agent as a cross-linked point is formed, the cross-linked density of the polyvinyl chloride base material is further improved, the heat resistance of the polyvinyl chloride base material is further enhanced, and the prepared polyvinyl chloride plastic has good mechanical properties such as tensile strength by utilizing the characteristics of high strength and high toughness of ramie fibers. In addition, the nano calcium carbonate in the wear-resistant auxiliary agent can form a special ball structure, so that the prepared polyvinyl chloride plastic has excellent wear resistance.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the abrasion resistant additive of example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The wear-resistant plastic with the ageing resistance comprises the following raw materials in parts by weight: 60 parts of polyvinyl chloride base stock, 2 parts of wear-resistant auxiliary agent, 5 parts of plasticizer dioctyl phthalate, 4 parts of lubricant stearic acid, 1 part of liquid calcium zinc stabilizer and 2 parts of flame retardant ammonium polyphosphate;
the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride base stock, wear-resistant auxiliary agent, lubricant stearic acid, liquid calcium zinc stabilizer and flame retardant ammonium polyphosphate into a stirring kettle in parts by weight, and stirring for 30min at a stirring rate of 500r/min to form premix;
step two: adding plasticizer dioctyl phthalate into the premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each area of the extruder to be 100 ℃ and the screw rotation speed to be 20r/min, and extruding and granulating to obtain the wear-resistant plastic.
The preparation method of the polyvinyl chloride base material comprises the following steps:
step (1): mixing 5g of polyvinyl chloride powder with chloroform, uniformly stirring, adding 12g of DL-cysteine and 16g of potassium carbonate, stirring uniformly, introducing nitrogen to deoxidize, stirring at 60 ℃ for 16 hours, cooling the materials, pouring the materials into methanol for precipitation, filtering and separating solid materials, washing, and drying in vacuum to obtain an intermediate material;
weighing 1g of intermediate sample, soaking in 50mL of 0.1M calcium acetate solution, ultrasonically oscillating for 30min, transferring 20mL of oscillating liquid, adding cresol red and thymol blue as indicators, titrating with 0.1M sodium hydroxide standard solution until the color of the solution changes, recording the volume V consumed by the sodium hydroxide standard solution, simultaneously performing a blank control test, recording the volume V1 of the sodium hydroxide standard solution consumed by the blank test, and using the formulaCalculating the carboxyl content in the sample, wherein C is the concentration (mol/L) of a sodium hydroxide standard solution; m is the sample mass (g); the carboxyl content of the sample was 1.214% as tested.
Step (2): 3g of intermediate material is mixed with ethanol, after being stirred uniformly, 1.2g of 3, 5-di-tert-butyl-4-hydroxy benzyl alcohol, 0.1g of 4-dimethylaminopyridine and 0.5g of dicyclohexylcarbodiimide compound are added into the system, after being mixed uniformly, under the protection of nitrogen, stirring is carried out at room temperature for 16 hours, the materials are poured into methanol for precipitation, solid materials are separated, washed and dried in vacuum, and the polyvinyl chloride base stock is obtained.
And (2) using the same test method as in the step (1), taking 1g of polyvinyl chloride base stock sample, and testing the carboxyl content of the polyvinyl chloride base stock sample to be 0.682%, wherein the carboxyl content in the polyvinyl chloride base stock sample is caused by esterification condensation reaction of carboxyl in an intermediate structure and benzyl alcohol groups in a 3, 5-di-tert-butyl-4-hydroxy benzyl alcohol structure, so that a large amount of carboxyl is consumed.
The preparation method of the wear-resistant auxiliary agent comprises the following steps:
step (1): adding 6g of ramie fibers into 15% sodium hydroxide solution by mass fraction, soaking for 24 hours, filtering and separating solid materials, washing to be neutral by using purified water, and vacuum drying to obtain alkali treated ramie fibers, wherein the length is 1mm, and the average diameter is 50um;
step (2): adding 1g of nano calcium carbonate into toluene, uniformly dispersing by ultrasonic, adding 3g of 3-isocyanatopropyl triethoxysilane, stirring uniformly, stirring at room temperature for 8 hours, centrifuging to separate a solid product, and drying in vacuum to obtain isocyanated nano calcium carbonate, wherein the particle size of the nano calcium carbonate is less than or equal to 100nm;
step (3): mixing 0.5g of isocyanated nano calcium carbonate with absolute ethyl alcohol, uniformly dispersing by ultrasonic, adding 2g of alkali-treated ramie fibers and 0.01g of dibutyltin dilaurate, continuing to act for 30min, raising the system temperature to 65 ℃, stirring for 18h at constant temperature, centrifugally separating solid materials, washing, and drying in vacuum to obtain the wear-resistant auxiliary agent.
The abrasion-resistant auxiliary agent is subjected to scanning electron microscope test, the test result is shown in figure 1, and as can be seen from figure 1, the abrasion-resistant auxiliary agent is a compound of ramie fibers and nano calcium carbonate, and the nano calcium carbonate is relatively uniformly dispersed on the surfaces of the ramie fibers.
Example 2
The wear-resistant plastic with the ageing resistance comprises the following raw materials in parts by weight: 75 parts of polyvinyl chloride base stock, 4 parts of wear-resistant auxiliary agent, 6 parts of trioctyl trimellitate serving as plasticizer, 5 parts of polyethylene wax serving as lubricant, 1.5 parts of liquid calcium-zinc stabilizer and 3 parts of ammonium polyphosphate serving as flame retardant;
the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride base stock, wear-resistant auxiliary agent, lubricant polyethylene wax, liquid calcium zinc stabilizer and flame retardant ammonium polyphosphate into a stirring kettle in parts by weight, and stirring for 40min at a stirring rate of 800r/min to form premix;
step two: adding trioctyl trimellitate serving as a plasticizer into a premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each region of the extruder to be 120 ℃, and extruding and granulating at the screw speed of 30r/min to obtain the wear-resistant plastic.
Wherein the polyvinyl chloride base material and the wear-resistant auxiliary agent were prepared in the same manner as in example 1.
Example 3
The wear-resistant plastic with the ageing resistance comprises the following raw materials in parts by weight: 80 parts of polyvinyl chloride base stock, 5 parts of wear-resistant auxiliary agent, 10 parts of tributyl citrate serving as plasticizer, 8 parts of lubricant paraffin, 2 parts of liquid calcium zinc stabilizer and 6 parts of flame retardant ammonium polyphosphate;
the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride base stock, wear-resistant auxiliary agent, lubricant polyethylene wax, liquid calcium zinc stabilizer and flame retardant ammonium polyphosphate into a stirring kettle in parts by weight, and stirring for 60min at a stirring rate of 1000r/min to form premix;
step two: adding a plasticizer tributyl citrate into the premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each area of the extruder to be 140 ℃ and the screw rotation speed to be 30r/min, and carrying out extrusion granulation to obtain the wear-resistant plastic.
Wherein the polyvinyl chloride base material and the wear-resistant auxiliary agent were prepared in the same manner as in example 1.
Comparative example 1
The wear-resistant plastic comprises the following raw materials in parts by weight: 75 parts of polyvinyl chloride resin, 4 parts of wear-resistant auxiliary agent, 6 parts of trioctyl trimellitate serving as plasticizer, 5 parts of polyethylene wax serving as lubricant, 1.5 parts of liquid calcium-zinc stabilizer and 3 parts of ammonium polyphosphate serving as flame retardant;
the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride resin, an abrasion-resistant auxiliary agent, a lubricant polyethylene wax, a liquid calcium zinc stabilizer and a flame retardant ammonium polyphosphate into a stirring kettle in parts by weight, and stirring for 40min at a stirring rate of 800r/min to form a premix;
step two: adding trioctyl trimellitate serving as a plasticizer into a premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each region of the extruder to be 120 ℃, and extruding and granulating at the screw speed of 30r/min to obtain the wear-resistant plastic.
Wherein the preparation method of the wear-resistant auxiliary agent is the same as that of the example 1.
Comparative example 2
The wear-resistant plastic comprises the following raw materials in parts by weight: 75 parts of polyvinyl chloride base stock, 4 parts of nano calcium carbonate, 6 parts of trioctyl trimellitate serving as a plasticizer, 5 parts of polyethylene wax serving as a lubricant, 1.5 parts of a liquid calcium-zinc stabilizer and 3 parts of ammonium polyphosphate serving as a flame retardant;
the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride base stock, nano calcium carbonate, lubricant polyethylene wax, liquid calcium zinc stabilizer and flame retardant ammonium polyphosphate into a stirring kettle in parts by weight, and stirring for 40min at a stirring rate of 800r/min to form premix;
step two: adding trioctyl trimellitate serving as a plasticizer into a premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each region of the extruder to be 120 ℃, and extruding and granulating at the screw speed of 30r/min to obtain the wear-resistant plastic.
Wherein the polyvinyl chloride base material was prepared in the same manner as in example 1.
Comparative example 3
The plastic comprises the following raw materials in parts by weight: 75 parts of polyvinyl chloride base stock, 4 parts of ramie fibers, 6 parts of trioctyl trimellitate serving as a plasticizer, 5 parts of polyethylene wax serving as a lubricant, 1.5 parts of liquid calcium-zinc stabilizer and 3 parts of ammonium polyphosphate serving as a flame retardant;
the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride base stock, ramie fiber, lubricant polyethylene wax, liquid calcium zinc stabilizer and flame retardant ammonium polyphosphate into a stirring kettle, and stirring for 40min at a stirring rate of 800r/min to form premix;
step two: adding trioctyl trimellitate serving as a plasticizer into a premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each region of the extruder to be 120 ℃, and extruding and granulating at the screw speed of 30r/min to obtain the plastic.
Wherein the polyvinyl chloride base material was prepared in the same manner as in example 1.
Comparative example 4
The plastic comprises the following raw materials in parts by weight: 75 parts of polyvinyl chloride resin, 6 parts of trioctyl trimellitate serving as a plasticizer, 5 parts of polyethylene wax serving as a lubricant, 1.5 parts of a liquid calcium zinc stabilizer and 3 parts of ammonium polyphosphate serving as a flame retardant;
the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride resin, lubricant polyethylene wax, liquid calcium zinc stabilizer and flame retardant ammonium polyphosphate into a stirring kettle in parts by weight, and stirring for 40min at a stirring rate of 800r/min to form premix;
step two: adding trioctyl trimellitate serving as a plasticizer into a premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each region of the extruder to be 120 ℃, and extruding and granulating at the screw speed of 30r/min to obtain the plastic.
The plastics prepared in inventive examples 1-3 and comparative examples 1-4 were sheeted, cut into test specimens meeting specifications, and tested for the following properties:
setting test loading force as 1000N and rotating speed as 0.43m/s with reference to standard GB/T3960-2016, and testing friction coefficient of plastic; setting the tensile rate to be 100mm/min by referring to the standard GB/T1040.1-2018, testing the tensile strength of the plastic, placing the plastic in an oven at 150 ℃ after the test is finished, performing an accelerated ageing test for 12 hours, testing the tensile strength of the plastic again, and evaluating the ageing resistance of the plastic; testing the impact strength of the plastic with reference to standard GB/T1843-2008; the Vicat softening temperature of the plastic was tested with reference to standard GB/T1633-2000, the test results are given in the following Table:
from the data presented in the above table, the plastics prepared in examples 1 to 3 according to the invention have good abrasion resistance, ageing resistance, mechanical and heat resistance properties.
The plastic prepared in the comparative example 1 uses the conventional polyvinyl chloride resin as a base material, does not contain hindered phenol groups, does not contain imino groups and the like in the structure, cannot interact with the wear-resistant auxiliary agent, and improves the crosslinking density of the polyvinyl chloride, so that the friction coefficient can be expressed, but the mechanical property, the ageing resistance and the heat resistance are reduced in different degrees.
The plastic prepared in comparative example 2 uses nano calcium carbonate as an abrasion-resistant additive, and because the nano calcium carbonate is not subjected to surface modification, agglomeration possibly occurs to a certain extent in the base material, so that the abrasion resistance is poor, and the unmodified nano calcium carbonate cannot be used as a crosslinking point and exists in the polyvinyl chloride base material, so that the mechanical properties and the heat resistance of the prepared plastic are also reduced to different extents.
The plastic prepared in the comparative example 3 uses the ramie fiber as the wear-resistant auxiliary agent, and the unmodified ramie fiber can only utilize the characteristics of high strength and high toughness of the ramie fiber to improve the mechanical properties of the plastic, but other properties are similar to those of the plastic in the comparative example 2, and the mechanical properties are reduced to different degrees.
The plastic prepared in comparative example 4 uses conventional polyvinyl chloride resin as the base material, and no abrasion-resistant auxiliary agent is added, so that each performance is the worst.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. The wear-resistant plastic with the ageing resistance is characterized by comprising the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride base stock, 2-5 parts of wear-resistant auxiliary agent, 5-10 parts of plasticizer, 4-8 parts of lubricant, 1-2 parts of stabilizer and 2-6 parts of flame retardant;
the polyvinyl chloride base material is polyvinyl chloride grafted with hindered phenol groups in the structure;
the wear-resistant auxiliary agent is a compound of nano calcium carbonate and ramie fibers.
2. The wear-resistant plastic with ageing resistance according to claim 1, wherein the plasticizer is any one of dioctyl phthalate, trioctyl trimellitate or tributyl citrate; the lubricant is any one of stearic acid, paraffin wax or polyethylene wax; the stabilizer is a liquid calcium-zinc stabilizer; the flame retardant is ammonium polyphosphate.
3. The wear-resistant plastic with ageing resistance according to claim 1, wherein the preparation method of the polyvinyl chloride base stock comprises the following steps:
step (1): mixing polyvinyl chloride powder with chloroform, stirring uniformly, adding DL-cysteine and an acid binding agent, stirring uniformly, introducing nitrogen to remove oxygen, stirring at 55-60 ℃ for 12-24 hours, cooling the materials, pouring the materials into methanol for precipitation, filtering and separating solid materials, washing, and drying in vacuum to obtain an intermediate material;
step (2): mixing the intermediate material with ethanol, stirring uniformly, adding 3, 5-di-tert-butyl-4-hydroxybenzyl alcohol and a composite catalyst into the system, stirring at room temperature for 12-18h under the protection of nitrogen, pouring the material into methanol for precipitation, separating out solid materials, washing, and drying in vacuum to obtain the polyvinyl chloride base material.
4. A wear resistant plastic with anti-aging properties according to claim 3, wherein in step (1), the acid binding agent is any one of sodium carbonate and potassium carbonate.
5. A wear resistant plastic with aging resistance according to claim 3, wherein in step (2), the composite catalyst is a 4-dimethylaminopyridine and dicyclohexylcarbodiimide composite, and the mass ratio of 4-dimethylaminopyridine to dicyclohexylcarbodiimide is 0.2-0.35:1.
6. The wear-resistant plastic with ageing resistance according to claim 1, wherein the preparation method of the wear-resistant additive comprises the following steps:
step (1): adding nano calcium carbonate into toluene, uniformly dispersing by ultrasonic, adding 3-isocyanatopropyl triethoxysilane, stirring uniformly, stirring at room temperature for 6-12h, centrifuging to separate a solid product, and drying in vacuum to obtain isocyanated nano calcium carbonate;
step (2): mixing isocyanated nano calcium carbonate with absolute ethyl alcohol, uniformly dispersing by ultrasonic, adding alkali-treated ramie fibers and dibutyl tin dilaurate, continuing to stand for 20-30min, raising the system temperature to 60-70 ℃, stirring at constant temperature for 12-24h, centrifugally separating solid materials, washing, and drying in vacuum to obtain the wear-resistant auxiliary agent.
7. The anti-aging wear-resistant plastic according to claim 6, wherein in the step (1), the particle size of the nano calcium carbonate is less than or equal to 100nm.
8. The abrasion-resistant plastic with aging resistance according to claim 6, wherein in the step (2), the alkali-treated ramie fiber is prepared by the following steps: soaking ramie fiber in 5-15% sodium hydroxide solution for 20-30 hr, filtering to separate solid material, washing with purified water to neutrality, and vacuum drying.
9. The abrasion resistant plastic with aging resistance according to claim 8, wherein the length of the ramie fibers is 1-2mm and the average diameter is 50um.
10. The wear-resistant plastic with ageing resistance according to claim 1, wherein the preparation method of the wear-resistant plastic comprises the following steps:
step one: adding polyvinyl chloride base stock, wear-resistant auxiliary agent, lubricant, stabilizer and flame retardant in parts by weight into a stirring kettle, and stirring for 30-60min at a stirring rate of 500-1000r/min to form premix;
step two: adding the plasticizer into the premix, uniformly mixing, transferring the mixed materials into a double-screw extruder, setting the temperature of each area of the extruder to be 100-140 ℃ and the screw rotation speed to be 20-30r/min, and carrying out extrusion granulation to obtain the wear-resistant plastic.
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| CN116855021B (en) * | 2023-09-05 | 2023-11-14 | 山东骏昂新材料科技有限公司 | Formula and production process of wear-resistant plastic part |
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