CN114163599A - Special high-flame-retardancy polyurethane plastic particles for indoor high-temperature ground mat and preparation method thereof - Google Patents
Special high-flame-retardancy polyurethane plastic particles for indoor high-temperature ground mat and preparation method thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 58
- 239000004814 polyurethane Substances 0.000 title claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 49
- 229920003023 plastic Polymers 0.000 title claims abstract description 46
- 239000004033 plastic Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 48
- 150000003077 polyols Chemical class 0.000 claims abstract description 48
- 239000003063 flame retardant Substances 0.000 claims abstract description 39
- 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 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 36
- 229920000570 polyether Polymers 0.000 claims abstract description 36
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000009736 wetting Methods 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004970 Chain extender Substances 0.000 claims abstract description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 34
- 239000004359 castor oil Substances 0.000 claims description 17
- 235000019438 castor oil Nutrition 0.000 claims description 17
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- -1 polyoxypropylene Polymers 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000012188 paraffin wax Substances 0.000 claims description 10
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 241001112258 Moca Species 0.000 claims description 2
- 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 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 229920000426 Microplastic Polymers 0.000 claims 1
- 238000006757 chemical reactions by type Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- SIEILFNCEFEENQ-UHFFFAOYSA-N dibromoacetic acid Chemical compound OC(=O)C(Br)Br SIEILFNCEFEENQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WMKYSVJWQJOFAN-IWQZZHSRSA-N (z)-2,3-dibromoprop-2-en-1-ol Chemical compound OC\C(Br)=C\Br WMKYSVJWQJOFAN-IWQZZHSRSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of polyurethane, and particularly relates to a high-flame-retardancy polyurethane plastic particle special for an indoor high-temperature ground mat and a preparation method thereof, wherein the polyurethane plastic particle is prepared from a component A and a component B, wherein: the component A comprises: polyether polyol, a chain extender, a plasticizer, a filler, a pigment, an anti-settling agent, a water removing agent, a catalyst, a defoaming agent and a wetting dispersant; the component B comprises: polyether polyol, isocyanate, a silane coupling agent, a plasticizer, an antioxidant and a flame retardant. The high-flame-retardant polyurethane plastic particles special for the indoor high-temperature ground mat have the characteristics of environmental protection, low odor, high strength, good cohesiveness and good flame retardance; the limit of harmful substances of the solid raw material in GB36246-2018 is met; the prepared ground mat has excellent flame retardant property and excellent mechanical property; the invention also provides a simple and feasible preparation method, is scientific, reasonable, simple and feasible, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to high-flame-retardancy polyurethane plastic particles special for an indoor high-temperature ground mat and a preparation method thereof.
Background
Polyurethane is a new organic polymer material, is known as 'fifth major plastic', is widely applied to various fields due to excellent performance, and the product application field relates to light industry, chemical industry, electronics, textiles, medical treatment, buildings, national defense, aerospace and the like. The polyurethane for paving becomes a main member of polyurethane materials, and mainly relates to polyurethane plastic tracks, silicon PU (polyurethane) courts, rubber ground mats, anti-skid pavements, waterproof materials and the like. The rubber floor mat is mainly used for paving the ground in kindergartens, school playgrounds, gymnasiums, leisure rooms, villas and the like, can reduce the hardness of the ground surface, is more comfortable and safer to walk, and can make the ground more vigorous and attractive through the matching of the rubber floor mats with different colors. The rubber floor mat is generally divided into an indoor floor mat and an outdoor floor mat, and the thickness of the rubber floor mat is generally 2-10 cm. The rubber floor mat is prepared by mixing polyurethane adhesive and particles and then pressing at high temperature, the mold temperature is generally 120-160 ℃, and the rubber floor mat can be pressed into various shapes according to requirements.
At present, most of particles used for rubber ground mats are rubber particles, EPDM particles or polyurethane plastic particles, and the mass of the particles is uneven. The most commonly used black rubber particles are mostly recycled tire particles, have relatively large pungent smell when used in indoor environment, are easy to burn, generate a large amount of toxic smoke during burning, and bring very large obstruction to escape personnel. The EPDM particles and the polyurethane plastic particles are mostly used for plastic runways and matched with polyurethane slurry or glue for use. Flame resistant particles are rare. According to statistics, all the particles used at present belong to flammable organic matters, fire is feared during use, once a fire disaster occurs, the rubber floor mat can become flammable matters and emit thick smoke to become toxic substances, particularly black rubber particles, the escape of people is hindered, and the environment and human bodies are seriously affected and injured. The flame retardancy and environmental protection of the particles are a great obstacle to the development of high-temperature mats for indoor use.
Disclosure of Invention
The invention aims to solve the technical problems of flame retardance and environmental protection of particles for high-temperature ground mats, overcomes the defects in the prior art, and provides high-flame-retardance polyurethane plastic particles special for indoor high-temperature ground mats, wherein the prepared ground mats have excellent flame retardance and environmental protection and also have excellent mechanical properties; the invention also provides a simple and feasible preparation method.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
the special high-flame-retardant polyurethane plastic particles for the indoor high-temperature ground mat are prepared from a component A and a component B, wherein:
the component A comprises the following raw materials in percentage by weight:
the component B comprises the following raw materials in percentage by weight:
the polyether polyol is a mixture of castor oil-based flame-retardant polyether polyol and polyoxypropylene polyol, the polyoxypropylene polyol has the functionality of 2 or 3, and the number average molecular weight of 3000-5000 or more, preferably DL-4000, EP-3600 (Shandong Daihang chemical group company) or N330 (Jiangsu Zhongshan chemical Co., Ltd.); the polyoxypropylene polyol in the polyether polyol of the A component is preferably selected from the group consisting of 2: 1, MN3050 and N330, the polyoxypropylene polyol in the polyether polyol of the B component preferably being present in a mass ratio of 1:1, DL-4000 and N330.
The mixing mass ratio of the castor oil-based flame-retardant polyether polyol and the polyoxypropylene polyol in the polyether polyol of the component A is 1:2, and the mixing mass ratio of the castor oil-based flame-retardant polyether polyol and the polyoxypropylene polyol in the polyether polyol of the component B is 1: 1.
Preferably, the isocyanate is diphenylmethane diisocyanate.
Preferably, the filler is one or two of 400-mesh talcum powder or 600-mesh talcum powder; the pigment is iron oxide red.
Preferably, the chain extender is a mixture of MOCA and DETDA, and the mass ratio is preferably 2: 3.
preferably, the water removing agent is Zoldine MS-Plus, and the anti-settling agent is organic bentonite; the catalyst is one of 2,4, 6-tri- (dimethylaminomethyl) phenol (Dabco TMR 30 of Air Products in the United states), dibutyltin dilaurate or bismuth isooctanoate. .
Preferably, the silane coupling agent is Z-6020(Dow Corning); the antioxidant is one or two of antioxidant Lowinox GP45 (Great Lakes chemical company, USA) or antioxidant 1010; the wetting dispersant was BYK-306 (Bick chemical, Germany); the defoamer was BYK-066N (Pyk chemical, Germany).
Preferably, the plasticizer is one or two of long-chain chlorinated paraffin or triethyl phosphate, and the mass ratio of the plasticizer to the plasticizer is preferably 2: 1 mixture of long-chain chlorinated paraffin and triethyl phosphate.
Preferably, the flame retardant is a2, 3-dibromo-2-propen-1-ol (2, 3-dibromoallyl alcohol or DBAA) reactive flame retardant.
The preparation method of the high-flame-retardant polyurethane plastic particles special for the indoor high-temperature ground mat comprises the following steps of:
preparation of component A:
putting polyether polyol and a plasticizer into a reaction kettle, starting stirring, adding a chain extender, a filler, a pigment and an anti-settling agent under a stirring state, heating to 90-100 ℃, carrying out vacuum dehydration to below 0.05%, sequentially adding a water removing agent, a wetting dispersant, a defoaming agent and a catalyst, and stirring for 30-40min to obtain a component A;
preparation of the component B:
putting isocyanate into a reaction kettle, starting stirring, adding polyoxypropylene polyol and a flame retardant at the temperature of 45 +/-5 ℃, heating to 80 +/-5 ℃ for 60min, preserving heat for 1.5h, adding castor oil-based flame-retardant polyether polyol, a silane coupling agent, the flame retardant and an antioxidant, keeping the temperature at 80 +/-5 ℃, reacting for 1.5h, sampling, detecting NCO%, and adding a plasticizer after NCO is qualified to prepare a component B;
preparation of polyurethane plastic particles
The prepared A, B components are mixed according to the mass ratio of 3: 1, tabletting, uniformly stirring in proportion, pouring into a high-temperature mould at 90-100 ℃, keeping the constant temperature for 20-30min, demoulding, curing in a drying room at 80 ℃ for 24h, and granulating to obtain the product.
The indoor high-temperature ground mat is prepared from the special high-flame-retardant polyurethane plastic particles for the indoor high-temperature ground mat, wherein the polyurethane plastic particles and the high-temperature adhesive are mixed according to the mass ratio of 100: 10, preparing the slices, then evenly mixing the slices, pouring the slices into a mold preheated to 145 ℃, pressing the slices into 5mm sample slices by a vulcanizing machine, and recording the mold opening time for later use. .
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention is a bi-component material, the reactive flame retardant is introduced into the component B, and the reactive flame retardant is uniformly grafted in the component B through an optimized production process, so that the effective flame retardant component in the system is improved, and the flame retardance is improved;
(2) the invention introduces the long-chain chlorinated paraffin and the triethyl phosphate plasticizer which have environmental protection and flame retardance at the same time, wherein the triethyl phosphate has stronger surface mobility, can form a high-flame-retardance film on the surface of a base material, and has better flame-retardant effect, no smoke, high temperature resistance and good chemical stability;
(3) according to the invention, the castor oil modified flame-retardant polyether is adopted, and A, B components are reasonably introduced at the same time, so that the mechanical property of the particles is ensured while the effective flame-retardant effect is ensured. The polyether polyol has high flame retardance and the advantages of narrow molecular weight distribution, low unsaturation degree and high molecular weight, and the products obtained by reasonably matching 2-functional polyoxypropylene polyol and 3-functional polyoxypropylene polyol have excellent high flame retardance and mechanical property.
(4) The preparation method is scientific, reasonable, simple and feasible, and is suitable for industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
(1) Putting polyether polyol MN 3050134 g, N33066 g, 100g of castor oil-based flame-retardant polyether polyol and 150g of long-chain chlorinated paraffin into a reaction kettle, starting stirring, adding MOCA32g, DETDA48g, 400-mesh talcum powder 300g, iron oxide red 100g and organic bentonite 30g under stirring, heating to 90-100 ℃, dehydrating under vacuum to below 0.05%, sequentially adding 10g of dehydrator, 10g of thickener, 10g of catalyst and 10g of wetting dispersant, stirring for 35min, and barreling to obtain the component A product.
(2) Putting 250g of diphenylmethane diisocyanate into a reaction kettle, starting stirring, adding 112.5g of DL-4000, 112.5g of N330 and 100g of DBAA at the temperature of 45 +/-5 ℃, heating to 80 +/-5 ℃ for 40min, preserving heat for 1.5h, adding 225g of castor oil-based flame-retardant polyether polyol, 60g Z-6020 and 15g of antioxidant 1010, keeping the temperature at 80 +/-5 ℃, reacting for 1.5h, sampling to detect NCO%, adding 62.5g of long-chain chlorinated paraffin and 62.5g of triethyl phosphate after the NCO is qualified, and barreling to obtain the B component product.
(3) The prepared A, B components are mixed according to the mass ratio of 3: 1, uniformly stirring the mixture in proportion, pouring the mixture into a high-temperature mold at the temperature of 90-100 ℃, keeping the constant temperature for 20-30min, demolding, curing the mixture in a drying room at the temperature of 80 ℃ for 24h, and cutting sample blocks into particles to prepare polyurethane plastic particles for later use.
(4) Mixing the prepared polyurethane plastic particles with a high-temperature adhesive according to the mass ratio of 100: 10, tabletting, pouring high-temperature adhesive and polyurethane plastic particles into a plastic beaker in proportion, uniformly stirring, pouring into a mold preheated to 145 ℃, pressing into a sample piece with the thickness of 5mm by using a vulcanizing machine, and recording the mold opening time for later use.
Example 2
(1) Putting 100g of polyether polyol MN 3050116 g, N33058 g, 86g of castor oil based flame-retardant polyether polyol and long-chain chlorinated paraffin into a reaction kettle, starting stirring, adding MOCA32g, DETDA48g, 400-mesh talcum powder 350g, iron oxide red 120g and organic bentonite 50g under stirring, heating to 90-100 ℃, dehydrating under vacuum to below 0.05%, sequentially adding 10g of dehydrator, 10g of thickener, 10g of catalyst and 10g of wetting dispersant, stirring for 30min, and barreling to obtain the component A product.
(2) Putting 200g of diphenylmethane diisocyanate into a reaction kettle, starting stirring, adding 137.5g of DL-4000, 137.5g of N330 and 50g of DBAA at the temperature of 45 +/-5 ℃, heating to 80 +/-5 ℃ for 40min, preserving heat for 1.5h, adding 275g of castor oil-based flame-retardant polyether polyol, 60g Z-6020 and 15g of antioxidant 1010, keeping the temperature at 80 +/-5 ℃, reacting for 1.5h, sampling to detect NCO%, adding 62.5g of long-chain chlorinated paraffin and 62.5g of triethyl phosphate after NCO is qualified, and barreling to obtain the B component product.
(3) The prepared A, B components are mixed according to the mass ratio of 3: 1, uniformly stirring the mixture in proportion, pouring the mixture into a high-temperature mold at the temperature of 90-100 ℃, keeping the constant temperature for 20-30min, demolding, curing the mixture in a drying room at the temperature of 80 ℃ for 24h, and cutting sample blocks into particles to prepare polyurethane plastic particles for later use.
(4) Mixing the prepared polyurethane plastic particles with a high-temperature adhesive according to the mass ratio of 100: 10, tabletting, pouring high-temperature adhesive and polyurethane plastic particles into a plastic beaker in proportion, uniformly stirring, pouring into a mold preheated to 145 ℃, pressing into a sample piece with the thickness of 5mm by using a vulcanizing machine, and recording the mold opening time for later use.
Example 3
Putting polyether polyol MN 3050124 g, N33063 g, castor oil based flame retardant polyether polyol 93g and long chain chlorinated paraffin 150g into a reaction kettle, starting stirring, adding MOCA20g, DETDA 30g, 400-mesh talcum powder 350g, iron oxide red 100g and organic bentonite 50g under stirring, heating to 90-100 ℃, vacuum dehydrating to below 0.05%, sequentially adding dehydrator 5g, thickener 5g, catalyst 5g and wetting dispersant 5g, stirring for 40min, and barreling to obtain the component A product.
(2) Putting 230g of diphenylmethane diisocyanate into a reaction kettle, starting stirring, adding 125g of DL-4000, 125g of N330 and 65g of DBAA at the temperature of 45 +/-5 ℃, heating to 80 +/-5 ℃ for 40min, preserving heat for 1.5h, adding 250g of castor oil-based flame-retardant polyether polyol, 40g Z-6020 and 15g of antioxidant 1010, keeping the temperature at 80 +/-5 ℃, reacting for 1.5h, sampling to detect NCO%, adding 75g of long-chain chlorinated paraffin and 75g of triethyl phosphate after NCO is qualified, and barreling to obtain the component B product.
(3) The prepared A, B components are mixed according to the mass ratio of 3: 1, uniformly stirring the mixture in proportion, pouring the mixture into a high-temperature mold at the temperature of 90-100 ℃, keeping the constant temperature for 20-30min, demolding, curing the mixture in a drying room at the temperature of 80 ℃ for 24h, and cutting sample blocks into particles to prepare polyurethane plastic particles for later use.
(4) Mixing the prepared polyurethane plastic particles with a high-temperature adhesive according to the mass ratio of 100: 10, tabletting, pouring high-temperature adhesive and polyurethane plastic particles into a plastic beaker in proportion, uniformly stirring, pouring into a mold preheated to 145 ℃, pressing into a sample piece with the thickness of 5mm by using a vulcanizing machine, and recording the mold opening time for later use.
Comparative example 1
(1) Putting polyether polyol MN 3050200 g, N330100 g and 150g of methyl chloropalmitolate into a reaction kettle, starting stirring, adding MOCA32g, DETDA48g, 300g of 400-mesh talcum powder, 100g of iron oxide red and 30g of organic bentonite under the stirring state, heating to 90-100 ℃, carrying out vacuum dehydration to below 0.05%, sequentially adding 10g of water removing agent, 10g of thickening agent, 10g of catalyst and 10g of wetting dispersant, stirring for 35min, and barreling to obtain a component A product.
(2) Putting 250g of diphenylmethane diisocyanate into a reaction kettle, starting stirring, adding 225g of DL-4000 and 225g of N330 at the temperature of 45 +/-5 ℃, heating to 80 +/-5 ℃ for 40min, adding 60g Z-6020 and 15g of antioxidant 1010, keeping the temperature at 80 +/-5 ℃, reacting for 2.5h, sampling to detect NCO%, adding 125g of methyl chloropalmitolate after the NCO is qualified, and barreling to obtain the B component product.
(3) The prepared A, B components are mixed according to the mass ratio of 3: 1, uniformly stirring the mixture in proportion, pouring the mixture into a high-temperature mold at the temperature of 90-100 ℃, keeping the constant temperature for 20-30min, demolding, curing the mixture in a drying room at the temperature of 80 ℃ for 24h, and cutting sample blocks into particles to prepare polyurethane plastic particles for later use.
(4) Mixing the prepared polyurethane plastic particles with a high-temperature adhesive according to the mass ratio of 100: 10, tabletting, pouring the high-temperature adhesive and the polyurethane plastic particles into a plastic beaker in proportion, uniformly stirring, pouring into a mold preheated to 145 ℃, pressing into a sample sheet with the thickness of 10mm by using a vulcanizing machine, and recording the mold opening time for later use.
Physical properties of the products obtained in examples 1 to 3 and comparative example 1 were measured together with a sample of a commercially available high-temperature mat as comparative example 2, and the results are shown in Table 1.
Table 1 physical property test results
| Physical properties of the product | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Particle hardness (Shao A) | 75 | 73 | 70 | 73 | 75 |
| Elongation at Break (%) | 400 | 450 | 500 | 400 | 350 |
| Tensile Strength (MPa) | 3 | 3.2 | 3.8 | 3.3 | 2.5 |
| Tear Strength (KN/m) | 20 | 19 | 17 | 19 | 15 |
| Odor grade | 2 | 2 | 2 | 2 | 4 |
| Flame retardancy (burning spot diameter cm) | 1.5 | 2.3 | 2 | 6 | 8 |
As can be seen from Table 1, compared with the high-temperature ground mat on the market, the product has obvious physical property advantages, the isocyanate is diphenylmethane diisocyanate, the castor oil-based flame-retardant polyether polyol and the polyether polyol are matched, the product is high in environmental protection level, and the liquid and the finished product meet the chemical detection standard of GB 36246-2018. Meanwhile, through polyether screening, the castor oil-based flame-retardant polyether polyol and the plasticizer are matched, a product with high physical performance is obtained, a product with high flame-retardant performance can also be obtained, and the tensile strength and the elongation are not lower than those of the products in the same line. Meanwhile, the reactive flame retardant also has good flame retardance. Meanwhile, the hardness of the polyurethane plastic particles is relatively moderate, and better elasticity and comfort are provided.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. The utility model provides a special high flame retardant polyurethane plastic granule of indoor high temperature ground mat which characterized in that: is prepared from a component A and a component B, wherein:
the component A comprises the following raw materials in percentage by weight:
the component B comprises the following raw materials in percentage by weight:
the polyether polyol is a mixture of castor oil-based flame-retardant polyether polyol and polyoxypropylene polyol, and the polyoxypropylene polyol is one or more of 2 or 3 in functionality and 3000-5000 in number average molecular weight.
2. The special high-flame-retardancy polyurethane plastic particle for an indoor high-temperature ground mat as claimed in claim 1, wherein: the mixing mass ratio of the castor oil-based flame-retardant polyether polyol and the polyoxypropylene polyol in the polyether polyol of the component A is 1:2, and the mixing mass ratio of the castor oil-based flame-retardant polyether polyol and the polyoxypropylene polyol in the polyether polyol of the component B is 1: 1.
3. The special high-flame-retardancy polyurethane plastic particle for an indoor high-temperature ground mat as claimed in claim 1, wherein: the isocyanate is diphenylmethane diisocyanate.
4. The special high-flame-retardancy polyurethane plastic particle for an indoor high-temperature ground mat as claimed in claim 1, wherein: the filler is one or two of 400-mesh talcum powder or 600-mesh talcum powder; the pigment is iron oxide red.
5. The special high-flame-retardancy polyurethane plastic particle for an indoor high-temperature ground mat as claimed in claim 1, wherein: the chain extender is a mixture of MOCA and DETDA; the water removing agent is Zoldine MS-Plus, and the anti-settling agent is organic bentonite; the catalyst is one of 2,4, 6-tri- (dimethylaminomethyl) phenol, dibutyltin dilaurate or bismuth isooctanoate.
6. The special high-flame-retardancy polyurethane plastic particle for an indoor high-temperature ground mat as claimed in claim 1, wherein: the silane coupling agent is Z-6020; the antioxidant is one or two of antioxidant Lowinox GP45 or antioxidant 1010; the wetting dispersant is BYK-306; the defoaming agent is BYK-066N.
7. The special high-flame-retardancy polyurethane plastic particle for an indoor high-temperature ground mat as claimed in claim 1, wherein: the plasticizer is one or two of long-chain chlorinated paraffin or triethyl phosphate.
8. The special high-flame-retardancy polyurethane plastic particle for an indoor high-temperature ground mat as claimed in claim 1, wherein: the flame retardant is a2, 3-dibromo-2-propylene-1-alcohol reaction type flame retardant.
9. A method for preparing the high flame-retardant polyurethane plastic particles special for indoor high-temperature ground mats as claimed in any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
preparation of component A:
putting polyether polyol and a plasticizer into a reaction kettle, starting stirring, adding a chain extender, a filler, a pigment and an anti-settling agent under a stirring state, heating to 90-100 ℃, carrying out vacuum dehydration to below 0.05%, sequentially adding a water removing agent, a wetting dispersant, a defoaming agent and a catalyst, and stirring for 30-40min to obtain a component A;
preparation of the component B:
putting isocyanate into a reaction kettle, starting stirring, adding polyoxypropylene polyol and a flame retardant at the temperature of 45 +/-5 ℃, heating to 80 +/-5 ℃ for 60min, preserving heat for 1.5h, adding castor oil-based flame-retardant polyether polyol, a silane coupling agent, the flame retardant and an antioxidant, keeping the temperature at 80 +/-5 ℃, reacting for 1.5h, sampling, detecting NCO%, and adding a plasticizer after NCO is qualified to prepare a component B;
preparation of polyurethane plastic particles
The prepared A, B components are mixed according to the mass ratio of 3: 1, tabletting, uniformly stirring in proportion, pouring into a high-temperature mould at 90-100 ℃, keeping the constant temperature for 20-30min, demoulding, curing and granulating to obtain the product.
10. An indoor high temperature ground mat which characterized in that: the special high-flame-retardancy polyurethane plastic particle for the indoor high-temperature ground mat, which is prepared by adopting the special high-flame-retardancy polyurethane plastic particle for the indoor high-temperature ground mat, is prepared by mixing the polyurethane plastic particle and a high-temperature adhesive according to the mass ratio of 100: 10, tabletting, pouring into a mold preheated to 145 ℃, and pressing by a vulcanizing machine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768250A (en) * | 2009-12-25 | 2010-07-07 | 山东东大一诺威聚氨酯有限公司 | High flame-retardant polyurethane composition and preparation method thereof |
| CN112409778A (en) * | 2020-10-30 | 2021-02-26 | 山东一诺威聚氨酯股份有限公司 | High-gel-content high-weather-resistance polyurethane plastic particle composition and preparation method thereof |
| CN112812731A (en) * | 2020-12-31 | 2021-05-18 | 山东一诺威聚氨酯股份有限公司 | High-flame-retardant high-temperature adhesive special for indoor high-temperature ground mat and method for preparing ground mat by using high-flame-retardant high-temperature adhesive |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768250A (en) * | 2009-12-25 | 2010-07-07 | 山东东大一诺威聚氨酯有限公司 | High flame-retardant polyurethane composition and preparation method thereof |
| CN112409778A (en) * | 2020-10-30 | 2021-02-26 | 山东一诺威聚氨酯股份有限公司 | High-gel-content high-weather-resistance polyurethane plastic particle composition and preparation method thereof |
| CN112812731A (en) * | 2020-12-31 | 2021-05-18 | 山东一诺威聚氨酯股份有限公司 | High-flame-retardant high-temperature adhesive special for indoor high-temperature ground mat and method for preparing ground mat by using high-flame-retardant high-temperature adhesive |
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