CN112300519A - MDI-DINP-based PVC cross-linking agent and PVC cross-linked material thereof - Google Patents
MDI-DINP-based PVC cross-linking agent and PVC cross-linked material thereof Download PDFInfo
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- CN112300519A CN112300519A CN202011257298.6A CN202011257298A CN112300519A CN 112300519 A CN112300519 A CN 112300519A CN 202011257298 A CN202011257298 A CN 202011257298A CN 112300519 A CN112300519 A CN 112300519A
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Links
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 78
- 239000011243 crosslinked material Substances 0.000 title description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 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 abstract description 33
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- 102100035474 DNA polymerase kappa Human genes 0.000 claims abstract description 20
- 101710108091 DNA polymerase kappa Proteins 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 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 description 18
- 239000003063 flame retardant Substances 0.000 claims description 18
- 229920002994 synthetic fiber Polymers 0.000 claims description 13
- 239000012209 synthetic fiber Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 27
- 239000002649 leather substitute Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 abstract description 5
- 239000010985 leather Substances 0.000 abstract description 4
- 238000012937 correction Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 230000000638 stimulation Effects 0.000 abstract description 2
- 238000005491 wire drawing Methods 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 72
- 229920000915 polyvinyl chloride Polymers 0.000 description 70
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229920001944 Plastisol Polymers 0.000 description 8
- 238000005187 foaming Methods 0.000 description 8
- 239000004999 plastisol Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000002969 artificial stone Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- -1 fatty acid ester Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002059 nanofabric Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Abstract
The invention discloses a MDI-DINP-based PVC cross-linking agent and a PVC cross-linking material thereof, wherein the cross-linking agent comprises 20-50 parts of diphenylmethane diisocyanate MDI; 50-100 parts of plasticizer DINP; 2-5 parts of catalyst phenol; 0.1 to 1 part of essence; the viscosity of the cross-linking agent is 2000mpas-6000 mpas; the NCO content is 3-30%. The cross-linking agent can be used for manufacturing high-end products such as tarpaulin, canvas, inflatable cushions, submachine boats, kayaks, wiredrawing cloth and the like, the manufactured products can meet the requirement of environmental protection, meet the correction instruction of European Union RoHS instruction 2011/65EU appendix II and the limit value requirement of (EU)2015/863, and can be used for manufacturing TPU artificial leather to replace PU artificial leather and PVC artificial leather. The product prepared by the cross-linking agent has the hand feeling similar to that of genuine leather, and has the advantages of long service life, good tearing strength and no stimulation.
Description
Technical Field
The invention relates to the technical field of crosslinking agents, in particular to a PVC crosslinking agent based on MDI-DINP.
Background
Polyvinyl chloride (PVC) paste resins are used, as their name implies, primarily in the form of a paste, commonly referred to as a plastisol, which is a unique liquid form of PVC plastic in its raw state. Paste resins are often prepared by emulsion and microsuspension processes.
The polyvinyl chloride paste resin has a fine particle size, is like talc in texture, and has no flowability. Polyvinyl chloride paste resins are mixed with plasticizers and stirred to form a stable suspension, i.e. to form a PVC paste, or PVC plastisol, PVC sol, and are used in this form for processing into finished products. During the paste making process, various fillers, diluents, heat stabilizers, foaming agents, light stabilizers and the like are added according to different product requirements.
The development of the PVC paste resin industry provides a new liquid material which becomes a polyvinyl chloride product upon heating only. The liquid material has the advantages of convenient preparation, stable performance, easy control, convenient use, excellent product performance, good chemical stability, certain mechanical strength, easy coloring and the like, thereby being widely applied to the production of artificial leather, vinyl toys, soft trademarks, wallpaper, paint coatings, foamed plastics and the like.
Polyvinyl chloride (PVC) paste resin belongs to a product branch of polyvinyl chloride resin. PVC paste resins are known for paste processing as highly dispersible powders. The paste forming performance is excellent, and the dispersion performance is good, so that the paste is mainly applied to the field of soft materials of PVC resin. The coating can be applied to the processing technologies of coating, dipping, spraying, foaming and the like, and can be widely applied to the fields of various materials and products such as artificial leather, decorative materials, floor leather, wall paper, industrial conveying belts, sports grounds, coatings, cross-linking agents, toys, medical disposable gloves, daily decorative materials, electrical instruments, electrical tools and the like.
The PVC paste resin molding processing has the advantages of low equipment price, simple and cheap processing mold, capability of being made into special shapes, easiness in foaming, few heating times of products, capability of producing a small amount of products in various varieties and the like, so that the PVC paste resin molding processing is widely applied to hard products such as artificial leather, floor leather, toys, wallpaper, automotive interior materials and the like, and has wide market application prospect.
From the above, it can be seen that the PVC paste resin has various uses. In the prior art, PVC paste resin has good bonding effect with coarse fibers such as cotton, but the surface of synthetic fibers is smooth and has no bonding effect on paste. Therefore, it is necessary to add a binder to the paste to improve the adhesion of the smooth surface synthetic fibers to the PVC paste resin.
The prior art discloses a method for preparing a composite material of PVC paste resin and fiber.
Document 1: CN201911216899.X discloses a flame-retardant waterproof and tarpaulin of nanometer PVC and a preparation method thereof, wherein the flame-retardant waterproof and tarpaulin of nanometer PVC is prepared by dipping and coating synthetic fiber base cloth with PVC nanometer flame-retardant plastisol, completely permeating tiny particles of nanometer penetrant into fiber gaps of the base cloth, flattening by a flattening machine, heating and plasticizing by an oven to prepare a cover film with flat and smooth two surfaces, and has good water permeability resistance. Solves the problems of water resistance, easy falling off of the tarpaulin covering film and skin breaking in the prior art. Synthetic vegetable fatty acid ester with flame retardant property and polishing slag with flame retardant and smoke suppression properties are added in the formula, so that the problem of flame retardant property reduction caused by the addition of a large amount of small-molecule plasticizer in the prior art is solved. The polishing slag is added as an inorganic filler in a large amount, so that the production cost is reduced, the flame retardant and smoke suppression performances of the PVC flame-retardant waterproof tarpaulin are improved, and the problems of environmental pollution caused by the fact that the polishing slag of stone materials, ceramic tiles and artificial stones is difficult to recycle and the waste landfill is solved.
Document 2: CN 201911216897.0; a flame-retarding and antistatic nano fabric for the wind tube is prepared through immersing synthetic fibre fabric in flame-retarding and antistatic PVC plastisols containing nano penetrant, pressing by flatting machine, heating in baking oven, plasticizing to obtain smooth covering film, and cooling. The plastisol completely permeates into the synthetic fiber, and the problem that the cover film is easy to fall off and the skin is broken to cause air leakage of the air duct in the prior art is solved. Synthetic vegetable fatty acid ester with flame retardant and antistatic properties and stone, ceramic tile and artificial stone polishing slag with flame retardant and smoke suppression properties are added in the formula, so that the problem of flame retardant property reduction caused by the addition of a large amount of small molecular plasticizers in the prior art is solved. The polishing slag is added in a large amount as an inorganic filler, so that the production cost is reduced, the flame retardant and smoke suppression performance of the product is improved, the problems that the polishing slag is difficult to recycle and the environment is polluted due to waste landfill are solved, and waste is changed into valuable.
Document 3: CN 201310506209.0; the artificial leather comprises a base material layer, an adhesive layer, a soft foaming layer and a mirror layer, wherein the adhesive layer is positioned between the base material layer and the soft foaming layer, and the mirror layer is positioned on the upper surface of the soft foaming layer. The manufacturing process method comprises the following steps: firstly, coating a bonding layer on a substrate layer, then coating and scraping PVC (polyvinyl chloride) plastisol on plain release paper to foam at high temperature and attach the PVC plastisol on the bonding layer, or directly coating the PVC plastisol on the substrate to foam at high temperature to prepare a soft foaming layer; then the mirror material is rolled and compounded on the surface of the soft foaming layer, and the high-performance soft composite mirror artificial leather is prepared. The invention solves the technical problem of modifying and processing the high-performance mirror-surface artificial leather by adopting the coating substrate for foaming and calendering the mirror surface, not only improves the softness of the mirror-surface artificial leather, but also improves the surface folding resistance, and has simple process.
It can be seen from the above documents that, in the prior art, no crosslinking agent is added in the process of compounding the PVC paste resin and the synthetic fiber, or the bonding effect of the crosslinking agent is poor. Based on the above, the technical problem to be solved by the present invention is to provide a crosslinking agent with better bonding effect in a longer time.
Disclosure of Invention
The invention aims to provide a PVC cross-linking agent based on MDI-DINP.
In order to achieve the above objects, one embodiment of the present invention provides a MDI-DINP based PVC crosslinking agent, comprising the following components:
diphenylmethane diisocyanate MDI: 20-50 parts of a solvent;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of catalyst phenol;
0.1 to 1 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3-30%.
In the optimized scheme of the invention, the cross-linking agent also comprises a stabilizing agent, a flame retardant and a terminating agent.
In the optimized scheme of the invention, the cross-linking agent comprises the following components:
diphenylmethane diisocyanate MDI: 20-30 parts;
plasticizer diisononyl phthalate DINP: 60-70 parts;
2.5 parts of catalyst phenol;
0.5 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3% -8%.
The invention also provides a method for preparing the PVC cross-linking agent according to the components, which comprises the following steps:
adding a plasticizer, namely diisononyl phthalate DINP and other auxiliary materials into a reaction kettle, heating to 120-140 ℃, dropwise adding diphenylmethane diisocyanate MDI (diphenylmethane diisocyanate) to react for 8-10 h, cooling after dropwise adding, filtering and discharging.
The invention also provides a PVC cross-linking material for bonding with the synthetic fiber, which comprises a PVC cross-linking agent and a PVC plasticizing paste, wherein 3-6% of the PVC cross-linking agent is added into each 100 parts of the PVC plasticizing paste;
wherein the PVC cross-linking agent comprises:
diphenylmethane diisocyanate MDI: 20-50 parts of a solvent;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of catalyst phenol;
0.1 to 1 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3% -30%;
wherein the PVC plasticizing paste comprises:
80-150 parts of PVC resin;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of stabilizer barium and zinc;
30-60 parts of calcium carbonate.
In summary, the invention has the following advantages:
1. the cross-linking agent can be used for improving the adhesive force of a substrate made of PVC speed-increasing sol coating polyester or polyamide aromatic fiber; the TP-300 type PVC cross-linking agent has stronger activity, and the reaction time between the sol coating and a substrate can be controlled in the PVC sol coating, namely the service life of a finished product is prolonged, and the longest service life can reach 5 years.
2. The invention can be used for manufacturing high-end products such as tarpaulin, canvas, inflatable cushions, submachine boats, canoes, wiredrawing cloth and the like.
3. The PVC paste resin material prepared by the cross-linking agent has good bonding characteristics of softness, tearing strength, peeling strength and opening time with higher reaction controllability and reliability.
4. The cross-linking agent prepared by the method is prepared into a product for detection, can meet the requirement of environmental protection, and has good light transmission, ageing resistance, strong low-temperature toughness, high resilience, good operability and convenient construction.
The cross-linking agent of the invention has the following characteristics:
1. the product of the invention is tested, wherein the test effects of cadmium, lead, mercury, hexavalent chromium, polybrominated diphenyl PBBS, polybrominated diphenyl ether PBDEs, lead phthalate, butyl benzyl phthalate and diisobutyl phthalate all meet the correction instruction of European Union RoHS instruction 2011/65EU appendix II and the limit requirement of (EU) 2015/863.
2. The cross-linking agent can be produced by rolling equipment and coating equipment commonly used in the industry. The cross-linking agent can be used for manufacturing TPU artificial leather to replace PU artificial leather and PVC artificial leather. The product prepared by the cross-linking agent has the hand feeling similar to that of genuine leather, and has the advantages of long service life, good tearing strength and no stimulation.
3. The product of the invention meets the requirement of environmental protection 3P, the molecular reaction period can be controlled for 60 months at most, and the outdoor product can be controlled for more than 120 months.
Detailed Description
The invention discloses a MDI-DINP (diphenyl diisocyanate-DiNP) -based PVC (polyvinyl chloride) crosslinking agent, which comprises the following components:
diphenylmethane diisocyanate MDI: 20-50 parts of a solvent;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of catalyst phenol;
0.1 to 1 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3-30%.
The cross-linking agent of the present invention further comprises a stabilizer, a flame retardant and a terminator.
Wherein, the stabilizer is 1 to 2 parts of methyl tin; 1-2 parts of flame retardant aluminum hydroxide; the terminating agent is dimethyl dithio-amino sodium formate, sodium polysulfide and sodium nitrite 0.01-0.1.
In the preferred embodiment of the invention, the proportion of each component is further limited, and the MDI-DINP-based PVC cross-linking agent is disclosed, and comprises the following components:
diphenylmethane diisocyanate MDI: 20-30 parts;
plasticizer diisononyl phthalate DINP: 60-70 parts;
2.5 parts of catalyst phenol;
0.5 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3% -8%.
The PVC cross-linking agent disclosed by the invention can be prepared by adopting the following method, and comprises the following steps:
adding a plasticizer, namely diisononyl phthalate DINP and other auxiliary materials into a reaction kettle, heating to 120-140 ℃, dropwise adding diphenylmethane diisocyanate MDI (diphenylmethane diisocyanate) to react for 8-10 h, cooling after dropwise adding, filtering and discharging.
Based on the PVC cross-linking agent disclosed by the invention, the invention also discloses a PVC cross-linking material bonded with the synthetic fiber by using the PVC cross-linking agent, which comprises the PVC cross-linking agent and PVC plasticizing paste, wherein 3-6% of the PVC cross-linking agent is added into each 100 parts of the PVC plasticizing paste;
wherein the PVC cross-linking agent comprises:
diphenylmethane diisocyanate MDI: 20-50 parts of a solvent;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of catalyst phenol;
0.1 to 1 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3% -30%;
wherein the PVC plasticizing paste comprises:
80-150 parts of PVC resin;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of stabilizer barium and zinc;
30-60 parts of calcium carbonate.
Example 1:
an MDI-DINP based PVC crosslinking agent comprises the following components:
diphenylmethane diisocyanate MDI: 30 parts of (1);
plasticizer diisononyl phthalate DINP: 80 parts of a mixture;
3 parts of catalyst phenol; 0.6 part of essence;
the viscosity of the cross-linking agent is 4000 mpas; the NCO content is 20%;
1 part of stabilizer methyl tin; 2 parts of flame retardant aluminum hydroxide;
0.03 part of terminator sodium dimethyldithiocarbamate.
Plasticizer diisononyl phthalate DINP, plasticizer diisononyl phthalate DINP: 80 parts of a mixture; 3 parts of catalyst phenol; 0.6 part of essence; the viscosity of the cross-linking agent is 4000 mpas; the NCO content is 20%; 1 part of stabilizer methyl tin; 2 parts of flame retardant aluminum hydroxide; adding 0.03 part of terminator sodium dimethyldithiocarbamate into a reaction kettle, heating to 120 ℃, dropwise adding diphenylmethane diisocyanate (MDI) for reacting for 8 hours, cooling after dropwise adding, filtering and discharging.
Example 2:
preparation of PVC plasticizing paste
100 parts of PVC paste resin;
plasticizer diisononyl phthalate DINP: 60 parts;
2.5 parts of stabilizer barium and zinc;
40 parts of calcium carbonate; the granularity is 800 meshes, and the moisture content is less than 0.3 percent.
The components are mixed evenly to obtain plasticized paste, and 3 to 6 percent of the PVC cross-linking agent is added into the plasticized paste to obtain the plasticized paste capable of being directly bonded with the synthetic fiber.
Experimental example 1: adhesion test
The experimental method comprises the following steps: adding the cross-linking agent into PVC plasticizing paste, wherein the addition amount of the cross-linking agent is 4.5%, and measuring the viscosity of the mixture by using an NDJ-1 type viscometer every 10min after adding the cross-linking agent, wherein the viscosity unit is mPa & s; the change in viscosity over 1h of crosslinker addition is shown in Table 1:
table 1: adhesion test results
| Time min | Viscosity mPas | Time of day | Viscosity of the oil |
| 0 | 3000 | 40 | 4150 |
| 10 | 3200 | 50 | 4300 |
| 20 | 3500 | 60 | 4420 |
| 30 | 3800 |
And (4) experimental conclusion:
the viscosity has a large influence on the production, and when the viscosity is extremely large or the rate of change of the viscosity is high, the production is liable to be adversely affected, and for example, when the change value of the viscosity within 1 hour is more than 10000 mPas, the industrial production is not suitable. The viscosity of the product prepared by the formula and the method is increased from 3000 to 4420 within 1h, and the product can meet the production requirement.
Experimental example 2: relationship between product molding time and peel strength
The experimental method comprises the following steps: the PVC plasticising paste obtained in example 2 was mixed with the cross-linking agent of the invention of example 1, the addition of which was 4.5%. After the cross-linking agent is added, the mixed material is uniformly coated on high-strength industrial polyester yarns made of synthetic fiber materials with 1100dtex and 1100dtex in both warp direction and weft direction by a scraper, the weaving density is 23 pieces/inch, the gram weight of the coating per square meter is controlled at 250g, and the polyester yarns are placed in a 200 ℃ oven for plasticizing for 1 min.
Cooling after plasticizing, cutting into five large sample blocks of 50cm by 200cm, carrying out heat sealing on the large sample blocks by using a high-frequency heat sealing machine, and then cutting into 4 small sample blocks;
then, the peel strength of each small sample block was measured using a universal tensile machine, and 4 small sample blocks were re-measured at intervals of 1 month during and after molding, respectively, with the measurement results shown in table 2:
table 2: detection results of peel strength of small sample blocks in different forming times
And (4) experimental conclusion:
after the cross-linking agent reacts with the PVC plasticizing paste, the peeling strength is improved in a long time after the cross-linking agent is formed with a synthetic fiber product.
According to the invention, the viscosity of the cross-linking agent is controlled to be 500-1200 by optimizing the formula and preparation process of the cross-linking agent, the reaction time of the cross-linking agent with a coating substrate and synthetic fibers is realized by controlling the viscosity of the cross-linking agent, so that the cross-linking agent can keep reacting with the substrate within 120 months at most, and the peel strength of the product is continuously improved along with time due to the continuous cross-linking action of the cross-linking agent in the slurry as the reaction is kept for a long time, thereby having good performance.
The reactivity of the cross-linking agent of the invention is very active, and how to control the viscosity of the reaction molecule under the condition that the reaction molecule is very active is one of the key technologies of the invention. According to the invention, through the adjustment of the formula process and the reaction period time, for example, the generation of the cross-linking agent of the invention is generally about 36 hours, and within the 36 hours, the viscosity of the cross-linking agent prepared by the invention can be controlled in an ideal state by controlling the temperature of the product and the adjustment of the formula.
Experimental example 3: environmental restriction detection
Category of detection: cadmium, lead, mercury, hexavalent chromium, polybrominated diphenyl ether and nitrobenzene plasticizers.
And (3) detection results: meets the correction instruction of EU ROHS 2011/65EU appendix two and the limit requirement of (EU) 2015/863.
The PVC cross-linking agent is a TP-300 type PVC cross-linking agent, is a single-component coating PVC cross-linking agent without toxic solvent, meets the environmental protection requirement of European Union, belongs to a phosphorus-free product, and is an environment-friendly product. The physical properties of the product are as follows:
appearance: white or light yellow emulsion, almost colorless, transparent liquid;
solid content: 95 percent;
viscosity: 2000mpas-6000 mpas;
specific gravity: 900 KGI;
NCO content: 3% -8% of common use, and 27% of maximum use;
hardness scale: softening;
gloss: and (4) bright light.
Claims (5)
1. An MDI-DINP based PVC crosslinking agent is characterized by comprising the following components:
diphenylmethane diisocyanate MDI: 20-50 parts of a solvent;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of catalyst phenol;
0.1 to 1 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3-30%.
2. The PVC crosslinking agent of claim 1, wherein: the cross-linking agent also comprises a stabilizing agent, a flame retardant and a terminating agent.
3. The PVC crosslinking agent of claim 1, wherein: comprises the following components:
diphenylmethane diisocyanate MDI: 20-30 parts;
plasticizer diisononyl phthalate DINP: 60-70 parts;
2.5 parts of catalyst phenol;
0.5 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3% -8%.
4. A process for preparing the PVC cross-linking agent of any one of claims 1 to 3, comprising the steps of:
adding a plasticizer, namely diisononyl phthalate DINP and other auxiliary materials into a reaction kettle, heating to 120-140 ℃, dropwise adding diphenylmethane diisocyanate MDI (diphenylmethane diisocyanate) to react for 8-10 h, cooling after dropwise adding, filtering and discharging.
5. A PVC cross-linking material used for bonding with synthetic fiber is characterized by comprising a PVC cross-linking agent and a PVC plasticizing paste, wherein 3-6% of the PVC cross-linking agent is added into each 100 parts of the PVC plasticizing paste;
wherein the PVC cross-linking agent comprises:
diphenylmethane diisocyanate MDI: 20-50 parts of a solvent;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of catalyst phenol;
0.1 to 1 part of essence;
the viscosity of the cross-linking agent is 2000mpas-6000 mpas;
the NCO content is 3% -30%;
wherein the PVC plasticizing paste comprises:
80-150 parts of PVC resin;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of stabilizer barium and zinc;
30-60 parts of calcium carbonate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683844A (en) * | 2021-08-26 | 2021-11-23 | 太原理工大学 | High-toughness polyvinyl chloride steel skeleton plastic dipping liquid and plastic dipping method thereof |
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