CN108129629B - Latex hand-feeling polyurethane soft foam and preparation method thereof - Google Patents
Latex hand-feeling polyurethane soft foam and preparation method thereof Download PDFInfo
- Publication number
- CN108129629B CN108129629B CN201611087490.9A CN201611087490A CN108129629B CN 108129629 B CN108129629 B CN 108129629B CN 201611087490 A CN201611087490 A CN 201611087490A CN 108129629 B CN108129629 B CN 108129629B
- Authority
- CN
- China
- Prior art keywords
- polyether polyol
- ethylene oxide
- polyurethane foam
- flexible polyurethane
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three 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
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
-
- 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
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a soft polyurethane foam with latex hand feeling and a preparation method thereof. The polyol combination used to prepare the flexible polyurethane foam comprises the following components: polyether polyol, water, a physical foaming agent, an amine catalyst, a tin catalyst, an organic silicon surfactant and a hand feeling promoter. The surface hardness of the polyurethane soft foam is less than 10A of Shore hardness, and the rebound resilience is more than 50%. Through the combination of polyether polyol and the use of a hand feeling accelerant, the problems that high resilience and high surface hardness coexist and low surface hardness, soft hand feeling and high resilience cannot be realized simultaneously in the prior art are solved.
Description
Technical Field
The invention relates to the field of polyurethane, in particular to a polyurethane soft foam with latex hand feeling.
Background
The polyurethane soft foam plastic, polyurethane soft foam for short, is a flexible polyurethane foam plastic with certain elasticity, and is a polyurethane product with the largest usage amount in polyurethane products.
The polyurethane soft foam is mainly of an open pore structure, has the performances of low density, good elastic recovery, sound absorption, ventilation, heat preservation and the like, is mainly used as cushion materials of furniture, mattresses, seats and cushions of vehicles and the like, and is also used as a filtering material, a sound insulation material, a shockproof material, a decorative material, a packaging material, a heat insulation material and the like in industry and civil use.
Latex bedding, particularly natural latex bedding, is a relatively new and sought-after product of the family bedding in recent years. The bedding has the characteristics of soft, smooth and comfortable foam surface, high foam resilience, good bearing capacity and the like, but because the bedding is regionally concentrated in the market and the protein in part of latex has sensitization on human bodies, more substitute products appear in the market.
The prior latex-like technology mostly adopts a polyolefin synthetic latex process, the foam is not breathable, mechanical punching is needed for assisting ventilation, and the comfort of the foam is poor after long-term use. Meanwhile, the olefin latex is crosslinked by sulfur, and the easy pulverization performance of foam is reduced under the illumination condition.
Compare in natural latex and synthetic latex bedding goods, the polyurethane goods have the gas permeability good, are difficult for breeding the bacterium, do not contain advantages such as sensitization material, resistant light straight penetrating, resistant sweat stain, nevertheless need to reach the advantage of latex goods, need the soft bubble of polyurethane to satisfy two conditions: (1) the foam surface hardness is low; (2) good foam elasticity and load bearing and good air permeability. CN102875768A adopts vegetable oil polyalcohol as raw material to obtain a simulated emulsion soft foam with the same hand feeling as high-density elastic polyurethane emulsion, and the method adopts more vegetable oil-based polyalcohol, thereby sacrificing the physical property of foam and improving the elasticity of the foam; CN203207611U and CN103222755A disclose latex-like sponge cushions, which are based on the conventional polyurethane sponge base, perforated to improve air permeability and surface comfort, and can not directly obtain excellent latex-like effect. Therefore, there is a need for a flexible polyurethane foam having a latex hand.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the soft polyurethane foam, which fundamentally improves the softness of the surface of the foam, improves the resilience and the air permeability of the foam and obtains the soft polyurethane foam which is closer to the hand feeling of latex by improving the formula.
In order to achieve the technical purpose, the invention provides the following technical scheme:
a soft polyurethane foam with latex hand feeling is prepared from raw materials including isocyanate component and polyol component; the weight ratio of the isocyanate component to the polyol component is from 0.4:1 to 1:1, preferably from 0.5:1 to 0.8: 1.
The polyol component of the present invention comprises the following components: the amount of each component is calculated by weight portion,
the isocyanate component of the present invention is preferably diisocyanate Y (NCO)2Wherein Y represents a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 15 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms. Suitable diisocyanates may be tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate, 1, 4-phenylene diisocyanate, toluene diisocyanate (isomers thereof include 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate), diphenylmethane diisocyanate (isomers thereof include 4,4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate), tetramethylxylene diisocyanate, hexamethylene diisocyanate, and, P-xylylene diisocyanate, p-isopropylidene diisocyanate and mixtures of these compounds.
Preferably, the isocyanate component of the present invention is selected from one or more of toluene diisocyanate, 4' -diphenylmethane diisocyanate; preferably, the weight ratio of 2, 4-toluene diisocyanate to 2, 6-toluene diisocyanate in the toluene diisocyanate is 80: 20 or 65: 35.
the polyether polyol is combined polyether and comprises the following components: the amount used is based on the total weight of the polyether polyol,
(1) the polyether polyol A has a hydroxyl value of from 10 to 40mgKOH/g, preferably from 20 to 35mgKOH/g, and a nominal functionality of from 3.0 to 3.5, preferably from 3.0 to 3.2, more preferably 3; the dosage is 50-95 wt%; preferably 70 wt% to 85 wt%;
(2) the polyether polyol B has a hydroxyl value of 200-400mgKOH/g, preferably 230-300mgKOH/g, and a nominal functionality of 3.0-4.0, preferably 3-3.5, more preferably 3.0; the amount is 4 wt% to 30 wt%, preferably 10 wt% to 20 wt%;
(3) the polyether polyol C has a hydroxyl value of from 20 to 50mgKOH/g, preferably from 30 to 40mgKOH/g, and a nominal functionality of from 2.8 to 3.2, preferably from 2.8 to 3.0, more preferably 2.8; the amount is 1 to 20 wt%, preferably 5 to 10 wt%.
The term nominal functionality is used herein to indicate the functionality (number of hydroxyl groups per molecule) of the polyether polyol. This is assumed to be the functionality (i.e. the number of active hydrogen atoms per molecule) of the initiator used in its preparation.
The initiator of the polyether polyol A is selected from glycerol and other small molecular polyols, and the other small molecular polyols comprise pentaerythritol and trimethylolpropane; the preferable polyether polyol A takes the glycerol with the content of 50 to 100 weight percent, preferably 80 to 100 weight percent in the initiator as the initiator; ethylene oxide and propylene oxide are copolymerized and synthesized by using polymerized monomers, the ethylene oxide is used for blocking, the content of the ethylene oxide in the polymerized monomers is 15 to 40 weight percent, preferably 20 to 30 weight percent, and the primary hydroxyl blocking rate of the polyether polyol A is 70 to 95 percent, preferably 80 to 90 percent. In the synthesis process of the polyether polyol A, the content of the ethylene oxide for end capping is at least 5 wt%, and the rest of the ethylene oxide is mixed with propylene oxide and then copolymerized.
The initiator of the polyether polyol B is selected from one or more of glycerol, pentaerythritol and trimethylolpropane, and preferably glycerol; propylene oxide is polymerized.
The initiator of the polyether polyol C is selected from one or more of glycerol, ethylene glycol, 1, 2-propylene glycol and pentaerythritol, preferably the mixture of the glycerol with the content of 80-100 wt%, preferably 90-100 wt% and the 1, 2-propylene glycol is used as the initiator; the ethylene oxide and the propylene oxide are copolymerized or synthesized by pure ethylene oxide polymerization, and the ethylene oxide is terminated, wherein the content of the ethylene oxide in the polymerization monomer is 50-100 wt%, preferably 60-80 wt%, and the primary hydroxyl termination rate of the polyether polyol C is 60-90%, preferably 70-80%. When the polyether polyol C is copolymerized by ethylene oxide and propylene oxide, the content of the ethylene oxide for end capping is at least 10 wt% in the synthesis process of the polyether polyol C, and the rest of the ethylene oxide is copolymerized after being mixed with the propylene oxide.
The physical foaming agent is selected from low-boiling-point solvents such as dichloromethane, butane, isobutane, pentane or cyclopentane, and the physical foaming agent is used for reducing the foam density and can reduce the foam framework strength through swelling a polymer so as to improve the foam openness.
The amine catalyst of the present invention is selected from one or more of diethylenetriamine, triethylenediamine, bis (2, 2-dimethylamino) ethyl ether, and tetramethyldiethylenetriamine.
The tin catalyst is selected from one or more of dibutyltin diacetate, stannous octoate and dibutyltin dilaurate.
The organic silicon surfactant is selected from colorless oily viscous transparent liquid which is formed by hydrolyzing chlorosilane to generate polysiloxane and condensing with polyether, and suitable examples include, but are not limited to, L618 of Michigan company, B8715 of winning company, AK7730 of Jiangsu Mesdie chemical industry Co.
The hand feeling accelerant is 2500-10000 meshes of calcium carbonate powder.
The invention also provides a preparation method of the polyurethane soft foam, which comprises the following steps: according to the proportion,
(1) uniformly mixing polyether polyol, water, a physical foaming agent, an amine catalyst, a tin catalyst, an organic silicon surfactant and a hand feeling promoter to obtain a polyol component, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) and (3) stirring and mixing the polyol component obtained in the step (1) and the isocyanate component obtained in the step (2), and pouring, foaming and maturing to obtain the polyurethane soft foam.
The surface hardness of the polyurethane soft foam is less than 10A of Shore hardness, and the rebound resilience is more than 50%.
Compared with the prior art, the invention has the beneficial effects that: the method has simple process and easy operation; the hand feeling accelerant and the polyether polyol are combined in the product components, so that the formula latitude of the product is increased, the hand feeling is improved, the resilience is increased, the production is stable, the problems that high resilience and high surface hardness coexist, low surface hardness, soft hand feeling and high resilience cannot be realized simultaneously in the prior art are solved, and the common problems that the formula latitude is narrow, the production is unstable, foams are closed and difficult to adjust are solved.
Detailed Description
The technical solution of the present invention is described in detail below, but the scope of the present invention is not limited to the embodiments.
The usage of the raw materials is weight portion.
The rebound resilience adopts a method for testing the rebound resilience by a ball drop method of GB/T6670-2008 soft foam polymer material.
The hand feeling is subjectively evaluated by non-label random drawing personnel, and is divided into 5 score levels, including: 1 very comfortable, 2 comfortable, 3 generally, 4 uncomfortable, 5 unacceptable. The mean was taken over 20 person assays.
Example 1
The polyether polyol component includes: 50 parts of polyether polyol A-1 (the initiator is glycerol and pentaerythritol in a weight ratio of 1:1, the nominal functionality is 3.4, the hydroxyl value is 10mgKOH/g, the propylene oxide content is 85 wt%, and the ethylene oxide content is 15 wt% (wherein, the randomly copolymerized ethylene oxide accounts for 10 wt% after being mixed with the propylene oxide, the ethylene oxide added into the system for primary hydroxyl end capping accounts for 5 wt% in the later polymerization stage), and the primary hydroxyl end capping rate is 70%); 30 parts of polyether polyol B-1 (the initiator is glycerol, the nominal functionality is 3, the hydroxyl value is 200mgKOH/g, and the content of propylene oxide is 100 wt%); 20 parts of polyether polyol C-1 (the initiator is glycerol and 1, 2-propylene glycol in a weight ratio of 8: 2, the nominal functionality is 2.8, the hydroxyl value is 20mgKOH/g, the propylene oxide content is 50 wt%, and the ethylene oxide content is 50 wt% (wherein, the ethylene oxide randomly copolymerized after being mixed with the propylene oxide accounts for 40 wt%, the ethylene oxide added into the system for primary hydroxyl end capping accounts for 10 wt% in the later period of polymerization), and the primary hydroxyl end capping rate is 60%).
The polyol component includes: 100 parts of polyether polyol component; 2 parts of water; 12 parts of a physical foaming agent (dichloromethane); 0.05 part of an amine catalyst (diethylenetriamine); 0.3 part of tin catalyst (dibutyltin diacetate); 0.5 part of silicone surfactant (Yingchuang company B8715); 10 portions of hand feeling accelerant (2500 meshes of calcium carbonate powder).
The isocyanate component is 4,4' -diphenylmethane diisocyanate.
The preparation method of the polyurethane soft foam comprises the following steps:
(1) uniformly mixing all substances in the polyol component according to the weight ratio, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) and (3) stirring and mixing the isocyanate component and the polyol component according to the weight ratio of 0.4:1, and pouring, foaming and maturing to obtain the polyurethane soft foam.
The foam surface hardness measured by a foam surface hardness tester is 6A (Shore A), the rebound resilience is 55%, and the hand feeling score is 1.2.
Example 2
The polyether polyol component includes: 95 parts of polyether polyol A-2 (initiator is glycerol and trimethylolpropane with the weight ratio of 8: 2, nominal functionality is 3.0, hydroxyl value is 40mgKOH/g, propylene oxide content is 60 wt%, and ethylene oxide content is 40 wt% (wherein ethylene oxide randomly copolymerized after being mixed with propylene oxide accounts for 35 wt%, ethylene oxide added into the system for primary hydroxyl end capping in the later polymerization stage accounts for 5 wt%), and primary hydroxyl end capping rate is 95%); 4 parts of polyether polyol B-2 (the initiator is trimethylolpropane, the nominal functionality is 3.0, the hydroxyl value is 400mgKOH/g, and the content of propylene oxide is 100 wt%); 1 part of polyether polyol C-2 (the initiator is glycerol and pentaerythritol in a weight ratio of 8: 2, the nominal functionality is 3.1, the hydroxyl value is 50mgKOH/g, the ethylene oxide content is 100 percent, and the primary hydroxyl end capping rate is 90 percent).
The polyol component includes: 100 parts of polyether polyol component; 5 parts of water; 0 part of physical foaming agent (butane); 0.3 part of amine catalyst (triethylene diamine); 0 part of tin catalyst (stannous octoate); 1.5 parts of a silicone surfactant (L618 of Meiji Co.); 1 part of hand feeling accelerant (10000 meshes of calcium carbonate powder).
The isocyanate component was toluene diisocyanate (2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate in a weight ratio of 80: 20).
The preparation method of the polyurethane soft foam comprises the following steps:
(1) uniformly mixing all substances in the polyol component according to the weight ratio, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) and (2) stirring and mixing the isocyanate component and the polyol component according to the weight ratio of 1:1, and pouring, foaming and maturing to obtain the polyurethane soft foam.
The foam surface hardness measured by a foam surface hardness tester is 9A (Shore A), the rebound resilience is 80 percent, and the hand feeling score is 1.3.
Example 3
The polyether polyol component includes: 70 parts of polyether polyol A-3 (the initiator is glycerol, the nominal functionality is 3.0, the hydroxyl value is 20mgKOH/g, the propylene oxide content is 80wt percent, and the ethylene oxide content is 20wt percent (wherein, the ethylene oxide randomly copolymerized after being mixed with the propylene oxide accounts for 15wt percent, the ethylene oxide added into the system for primary hydroxyl end capping accounts for 5wt percent in the later polymerization stage), and the primary hydroxyl end capping rate is 80 percent); 20 parts of polyether polyol B-3 (the initiator is glycerol, the nominal functionality is 3, the hydroxyl value is 230mgKOH/g, and the content of propylene oxide is 100 wt%); 10 parts of polyether polyol C-3 (the initiator is propylene glycol and 1, 2-propylene glycol in a weight ratio of 9: 1, the nominal functionality is 2.9, the hydroxyl value is 30mgKOH/g, the propylene oxide content is 40 wt%, and the ethylene oxide content is 60 wt% (wherein 48 wt% of randomly copolymerized ethylene oxide after being mixed with propylene oxide, 12 wt% of ethylene oxide added into the system for primary hydroxyl end capping at the later stage of polymerization, and 70% of primary hydroxyl end capping rate))
The polyol component includes: 100 parts of polyether polyol component; 3.5 parts of water; 6 parts of a physical foaming agent (isobutane); 0.17 part of amine catalyst (bis (2, 2-dimethylamino) ethyl ether); 0.15 part of a tin catalyst (dibutyltin dilaurate); 1.0 part of a silicone surfactant (AK 7730 available from Jiangsu Messaging chemical Co., Ltd.); 5.5 parts of hand feeling accelerant (7500 meshes of calcium carbonate powder).
The isocyanate component was toluene diisocyanate (weight ratio of 2, 4-toluene diisocyanate to 2, 6-toluene diisocyanate was 65: 35).
The preparation method of the polyurethane soft foam comprises the following steps:
(1) uniformly mixing all substances in the polyol component according to the weight ratio, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) mixing an isocyanate component and a polyol component in a weight ratio of 0.7: 1, and pouring, foaming and maturing to obtain the polyurethane soft foam.
The foam surface hardness measured by a foam surface hardness tester is 9A (Shore A), the rebound resilience is 70%, and the hand feeling score is 1.1.
Example 4
The polyether polyol component includes: 85 parts of polyether polyol A-4 (the initiator is glycerol and pentaerythritol in a weight ratio of 8: 2, the nominal functionality is 3.1, the hydroxyl value is 35mgKOH/g, the propylene oxide content is 70 wt%, and the ethylene oxide content is 30 wt% (wherein, the randomly copolymerized ethylene oxide accounts for 23 wt% after being mixed with the propylene oxide, the ethylene oxide added into the system for primary hydroxyl capping accounts for 7 wt% at the later stage of polymerization), and the primary hydroxyl capping rate is 90%); 10 parts of polyether polyol B-4 (the initiator is pentaerythritol, the nominal functionality is 4, the hydroxyl value is 300mgKOH/g, and the content of propylene oxide is 100 wt%); 5 parts of polyether polyol C-4 (the initiator is glycerol, the nominal functionality is 3.0, the hydroxyl value is 40mgKOH/g, the propylene oxide content is 20 wt%, and the ethylene oxide content is 80 wt% (wherein, the randomly copolymerized ethylene oxide accounts for 65 wt% after being mixed with the propylene oxide, the ethylene oxide added into the system for primary hydroxyl end capping accounts for 15 wt% at the later stage of polymerization), and the primary hydroxyl end capping rate is 80%).
The polyol component includes: 100 parts of polyether polyol component; 3 parts of water; 10 parts of a physical foaming agent (cyclopentane); 0.3 part of an amine catalyst (tetramethyldiethylenetriamine); 0 part of tin catalyst (stannous octoate); 1.0 part of a silicone surfactant (L618 of Meiji Co.); 5 parts of hand feeling accelerant (5000 meshes of calcium carbonate powder).
The isocyanate component was toluene diisocyanate (weight ratio of 2, 4-toluene diisocyanate to 2, 6-toluene diisocyanate was 80: 20).
The preparation method of the polyurethane soft foam comprises the following steps:
(1) uniformly mixing all substances in the polyol component according to the weight ratio, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) mixing an isocyanate component and a polyol component in a weight ratio of 0.7: 1, and pouring, foaming and maturing to obtain the polyurethane soft foam.
The foam surface hardness measured by a foam surface hardness tester is 3A (Shore A), the rebound resilience is 50%, and the hand feeling score is 1.2.
Example 5
The polyether polyol component includes: 78 parts of polyether polyol A-5 (initiator is glycerol and pentaerythritol in a weight ratio of 8: 2, nominal functionality is 3.1, hydroxyl value is 27mgKOH/g, propylene oxide content is 75 wt%, and ethylene oxide content is 25 wt% (wherein, the randomly copolymerized ethylene oxide accounts for 18 wt% after being mixed with propylene oxide, and the ethylene oxide added into the system for primary hydroxyl capping accounts for 7 wt% in the later stage of polymerization), and the primary hydroxyl capping rate is 85%); 15 parts of polyether polyol B-5 (the initiator is glycerol, the nominal functionality is 3.0, the hydroxyl value is 270mgKOH/g, and the content of propylene oxide is 100 wt%); 7 parts of polyether polyol C-5 (the initiator is glycerol and 1, 2-propylene glycol in a weight ratio of 8: 2, the nominal functionality is 2.8, the hydroxyl value is 35mgKOH/g, the propylene oxide content is 30 wt%, and the ethylene oxide content is 70 wt% (wherein 58 wt% of randomly copolymerized ethylene oxide is mixed with propylene oxide, 12 wt% of ethylene oxide added into the system for primary hydroxyl capping at the later stage of polymerization), and the primary hydroxyl capping rate is 75%).
The polyol component includes: 100 parts of polyether polyol component; 3 parts of water; 8 parts of a physical foaming agent (cyclopentane); 0.3 part of an amine catalyst (tetramethyldiethylenetriamine); 0 part of tin catalyst (stannous octoate); 1.0 part of silicone surfactant (B8715 of winning and creating company); 5 parts of hand feeling accelerant (5000 meshes of calcium carbonate powder).
The isocyanate component is 4,4' -diphenylmethane diisocyanate.
The preparation method of the polyurethane soft foam comprises the following steps:
(1) uniformly mixing all substances in the polyol component according to the weight ratio, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) mixing an isocyanate component and a polyol component in a weight ratio of 0.8:1, and pouring, foaming and maturing to obtain the polyurethane soft foam.
The foam surface hardness measured by a foam surface hardness tester is 5A (Shore hardness A), the rebound resilience is 60 percent, and the hand feeling score is 1.2.
The foams prepared in examples 1-5 had no flatulence, no hard core, surface hardness lower than 15A (Shore hardness), resilience higher than 50%, comfortable and soft hand feeling, good air permeability, and no need of perforation for ventilation.
Comparative example 1
The polyol component includes: 100 parts of polyether polyol-1 (an initiator is glycerol, the nominal functionality is 3.0, the hydroxyl value is 28mgKOH/g, the content of propylene oxide is 80 wt%, the content of ethylene oxide is 20 wt% (wherein, the ethylene oxide randomly copolymerized after being mixed with the propylene oxide accounts for 15 wt%, the ethylene oxide added into a system for primary hydroxyl end capping accounts for 5 wt%, and the primary hydroxyl end capping rate is 80%) 4 parts of water, 6 parts of a physical foaming agent (dichloromethane), 0.08 part of an amine catalyst (triethylene diamine), 0.1 part of a tin catalyst (stannous octoate), 1 part of an organic silicon surfactant (B8715), and 0 part of a hand feeling accelerator.
The isocyanate component is 4,4' -diphenylmethane diisocyanate.
The preparation method of the polyurethane soft foam comprises the following steps:
(1) uniformly mixing all substances in the polyol component according to the weight ratio, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) and (3) stirring and mixing the isocyanate component and the polyol component according to the weight ratio of 0.6:1, casting, foaming and maturing to obtain the No. 1 sponge (high resilience foam).
The surface hardness of the sponge No. 1 was 20A (Shore A), and the rebound resilience was 60%.
Comparative example 2
The polyol component includes: 90 parts of polyether polyol-2 (the initiator is glycerol, the nominal functionality is 3.0, the hydroxyl value is 240mgKOH/g, the propylene oxide content is 100 wt%), 10 parts of polyether polyol C-5 (the initiator is glycerol and 1, 2-propylene glycol in a weight ratio of 8: 2, the nominal functionality is 2.8, the hydroxyl value is 35mgKOH/g, the propylene oxide content is 30 wt%, and the ethylene oxide content is 70 wt% (wherein 58 wt% of ethylene oxide randomly copolymerized after being mixed with propylene oxide, 12 wt% of ethylene oxide added to the system for primary hydroxyl group capping in the later stage of polymerization), 75% of primary hydroxyl group capping rate), 3.3 parts of water, 10 parts of a physical blowing agent (cyclohexane), 0.05 part of an amine catalyst (bis (2, 2-dimethylamino) ethyl ether), 0.15 part of a tin catalyst (stannous octoate), 1.5 parts of an organosilicon surfactant (L618), and 0 part of a hand feeling accelerator.
The isocyanate component was toluene diisocyanate (weight ratio of 2, 4-toluene diisocyanate to 2, 6-toluene diisocyanate was 80: 20).
The preparation method of the polyurethane soft foam comprises the following steps:
(1) uniformly mixing all substances in the polyol component according to the weight ratio, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) and (3) stirring and mixing the isocyanate component and the polyol component according to the weight ratio of 0.4:1, casting, foaming and maturing to obtain the No. 2 sponge (slow rebound foam).
The surface hardness of the No. 2 sponge is 8A (Shore hardness A), the rebound resilience is 0 percent, and the surface hardness and the rebound resilience of the conventional foam formula can not be considered at the same time.
Comparative example 3
The conditions were the same as in example 1 except that the hand feeling improver was not used. A # 3 sponge (simulated latex foam) was prepared.
The surface hardness is 4A (Shore A), the rebound resilience is 55%, and the hand feeling score is 2.6.
While the invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (13)
1. A soft polyurethane foam with latex hand feeling is prepared from raw materials including an isocyanate component and a polyol component, wherein the polyol component comprises the following components: the amount of each component is calculated by weight portion,
the weight ratio of the isocyanate component to the polyol component is from 0.4:1 to 1: 1;
the polyether polyol comprises the following components in amounts based on the total weight of the polyether polyol:
(1) the hydroxyl value of the polyether polyol A is 10-40mgKOH/g, and the nominal functionality is 3.0-3.5; 50-95 wt% of ethylene oxide and propylene oxide are copolymerized, the ethylene oxide is used for sealing the end, the content of the ethylene oxide in the polymerized monomer is 15-40 wt%, and the primary hydroxyl sealing rate is 70-95%;
(2) the hydroxyl value of the polyether polyol B is 200-400mgKOH/g, and the nominal functionality is 3.0-4.0; 4-30 wt% of propylene oxide;
(3) the hydroxyl value of the polyether polyol C is 20-50mgKOH/g, and the nominal functionality is 2.8-3.2; 1-20 wt% of ethylene oxide and propylene oxide are copolymerized and ethylene oxide is blocked or ethylene oxide is polymerized and synthesized, the content of ethylene oxide in the polymerized monomer is 50-100 wt%, and the blocking rate of primary hydroxyl is 60-90%;
the hand feeling accelerant is 2500-10000 meshes of calcium carbonate powder.
2. The flexible polyurethane foam according to claim 1, wherein the components are used in amounts of parts by weight,
the weight ratio of the isocyanate component to the polyol component is from 0.5:1 to 0.8: 1.
3. The flexible polyurethane foam according to claim 1, wherein the polyether polyol comprises the following components:
(1) the hydroxyl value of the polyether polyol A is 20-35mgKOH/g, and the nominal functionality is 3.0-3.2; the dosage is 70 wt% -85 wt%;
(2) the hydroxyl value of the polyether polyol B is 230-300mgKOH/g, and the nominal functionality is 3-3.5; the dosage is 10 wt% -20 wt%;
(3) the hydroxyl value of the polyether polyol C is 30-40mgKOH/g, and the nominal functionality is 2.8-3.0; the dosage is 5 wt% -10 wt%;
the amounts are based on the total weight of the polyether polyol.
4. The flexible polyurethane foam according to claim 1, wherein the content of glycerin in the initiator of the polyether polyol a is 50 to 100 wt%.
5. The flexible polyurethane foam according to claim 4, wherein the content of glycerin in the initiator of the polyether polyol A is 80 to 100 wt%; the content of the ethylene oxide in the polymerized monomer is 20-30 wt%, and the end capping rate of the primary hydroxyl is 80-90%.
6. The flexible polyurethane foam according to claim 1, wherein the initiator of the polyether polyol B is selected from one or more of glycerol, pentaerythritol and trimethylolpropane.
7. The flexible polyurethane foam according to claim 1, wherein the polyether polyol C is a mixture of glycerin and 1, 2-propylene glycol having a glycerin content of 80 to 100 wt% as an initiator.
8. The flexible polyurethane foam according to claim 7, wherein the polyether polyol C is a mixture of glycerin and 1, 2-propylene glycol having a glycerin content of 90 to 100 wt% as an initiator; the content of the ethylene oxide in the polymerized monomer is 60 to 80 weight percent, and the end capping rate of the primary hydroxyl is 70 to 80 percent.
9. The flexible polyurethane foam according to claim 1, wherein the physical blowing agent is selected from one or more of methylene chloride, butane, isobutane, pentane and cyclopentane.
10. The flexible polyurethane foam of claim 1, wherein the amine catalyst is selected from one or more of diethylenetriamine, triethylenediamine, bis (2, 2-dimethylamino) ethyl ether, and tetramethyldiethylenetriamine; the tin catalyst is selected from one or more of dibutyltin diacetate, stannous octoate and dibutyltin dilaurate.
11. The flexible polyurethane foam according to claim 1, wherein the isocyanate component is selected from one or more of toluene diisocyanate and 4,4' -diphenylmethane diisocyanate.
12. The flexible polyurethane foam according to claim 11, wherein the toluene diisocyanate comprises 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate in a weight ratio of 80: 20 or 65: 35.
13. a process for preparing the flexible polyurethane foam of any one of claims 1-12, comprising the steps of: according to the proportion,
(1) uniformly mixing polyether polyol, water, a physical foaming agent, an amine catalyst, a tin catalyst, an organic silicon surfactant and a hand feeling promoter to obtain a polyol component, and keeping the temperature at 20-25 ℃;
(2) keeping the temperature of the isocyanate component at 20-25 ℃;
(3) and (3) stirring and mixing the polyol component obtained in the step (1) and the isocyanate component obtained in the step (2), and pouring, foaming and maturing to obtain the polyurethane soft foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611087490.9A CN108129629B (en) | 2016-12-01 | 2016-12-01 | Latex hand-feeling polyurethane soft foam and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611087490.9A CN108129629B (en) | 2016-12-01 | 2016-12-01 | Latex hand-feeling polyurethane soft foam and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108129629A CN108129629A (en) | 2018-06-08 |
| CN108129629B true CN108129629B (en) | 2021-01-15 |
Family
ID=62387460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611087490.9A Active CN108129629B (en) | 2016-12-01 | 2016-12-01 | Latex hand-feeling polyurethane soft foam and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108129629B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614122B (en) * | 2018-06-20 | 2023-03-24 | 万华化学集团股份有限公司 | Preparation method of supported hydrosilylation catalyst |
| US11932722B2 (en) | 2018-10-08 | 2024-03-19 | Dow Global Technologies Llc | Formulated polyol compositions |
| CN109438666B (en) * | 2018-10-31 | 2021-09-28 | 湖南铁研博发科技有限公司 | Low-temperature-resistant and impact-resistant material and preparation method and application thereof |
| CN109762125A (en) * | 2019-01-17 | 2019-05-17 | 东莞市和信新材料科技有限公司 | A kind of nano anti-static polyurethane foam and preparation method thereof |
| CN110028650A (en) * | 2019-05-08 | 2019-07-19 | 惠州展亿科技有限公司 | A kind of polyurethane flexible foam and preparation method thereof containing latex |
| CN112708126B (en) * | 2020-12-14 | 2023-04-28 | 山东一诺威新材料有限公司 | Polyether polyol for imitation latex polyurethane foam and preparation method thereof, and low-temperature-resistant imitation latex foam and preparation method thereof |
| CN115286760A (en) * | 2022-09-15 | 2022-11-04 | 苏州市天利海绵有限公司 | Soft sponge and production method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010503740A (en) * | 2006-09-15 | 2010-02-04 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing rigid polyurethane foam |
| CN104031235A (en) * | 2013-03-05 | 2014-09-10 | 万华化学（北京）有限公司 | Preparation method of visco-elastic polyurethane sound-absorbing foam |
| CN104910552A (en) * | 2015-06-03 | 2015-09-16 | 厦门艺特卫浴有限公司 | Frosted hose formula |
-
2016
- 2016-12-01 CN CN201611087490.9A patent/CN108129629B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010503740A (en) * | 2006-09-15 | 2010-02-04 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing rigid polyurethane foam |
| CN104031235A (en) * | 2013-03-05 | 2014-09-10 | 万华化学（北京）有限公司 | Preparation method of visco-elastic polyurethane sound-absorbing foam |
| CN104910552A (en) * | 2015-06-03 | 2015-09-16 | 厦门艺特卫浴有限公司 | Frosted hose formula |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108129629A (en) | 2018-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108129629B (en) | Latex hand-feeling polyurethane soft foam and preparation method thereof | |
| CN104031235B (en) | A kind of preparation method of visco-elasticity polyurethane sound-absorbing foam | |
| CN102504175B (en) | Preparation method for low-density viscoelastic polyurethane foam | |
| JP4611291B2 (en) | Viscoelastic polyurethane foam | |
| JP5228914B2 (en) | Method for producing flexible polyurethane foam | |
| CN107857865B (en) | Full-water environment-friendly flame-retardant flatulence memory polyurethane foam for automobile seat and preparation method thereof | |
| JP5266756B2 (en) | Low resilience flexible polyurethane foam and method for producing the same | |
| CN1961016B (en) | Low-density polyurethane foam materials and their use in shoe soles | |
| CN109021193B (en) | MDI system high-breathability viscoelastic polyurethane foam and preparation method thereof | |
| CN109021205B (en) | Open-cell polyurethane slow-resilience foam and preparation method thereof | |
| CN110283293B (en) | Latex-like polyurethane soft foam prepared from isocyanate-terminated prepolymer | |
| JP4454627B2 (en) | Viscoelastic polyurethane foam | |
| CN109912763B (en) | Polyurethane composition, polyurethane foam and application thereof | |
| JP5393089B2 (en) | Molded urethane pad for vehicle seat, vehicle seat and manufacturing method thereof | |
| CN104403063A (en) | Organosilicon copolymer surfactant and application thereof | |
| JPH09176270A (en) | Polyol composition for producing latex-like flexible polyurethane foam | |
| JP2001502010A (en) | Polyol combination | |
| WO2001025305A1 (en) | Polyol combination | |
| CN113105664A (en) | Polyurethane foam stabilizer | |
| JPWO2013021871A1 (en) | Method for producing flexible polyurethane foam | |
| CN109293876A (en) | A kind of novel body building apparatus material and preparation method thereof | |
| CN115698114A (en) | Viscoelastic elastomer polyurethane foam, method for the production thereof and use thereof | |
| CN113461904A (en) | Soft, high-elasticity, water-absorbing and non-swelling polyether foam and preparation method thereof | |
| JPWO2012115113A1 (en) | Low resilience flexible polyurethane foam and method for producing the same | |
| JP2004231706A (en) | Seat cushion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ye Tian Inventor after: Wang Xinwei Inventor after: Ju Changxun Inventor after: Wang Jinghui Inventor after: Zhang Qinhua Inventor after: Yang Xi Inventor before: Ye Tian Inventor before: Ju Changxun Inventor before: Wang Jinghui Inventor before: Zhang Qinhua Inventor before: Yang Xi |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Latex felt soft polyurethane foam and preparation method thereof Effective date of registration: 20211123 Granted publication date: 20210115 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20210115 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |