CN110964309A - High-hardness sponge and processing technology thereof - Google Patents

High-hardness sponge and processing technology thereof Download PDF

Info

Publication number
CN110964309A
CN110964309A CN201911270845.1A CN201911270845A CN110964309A CN 110964309 A CN110964309 A CN 110964309A CN 201911270845 A CN201911270845 A CN 201911270845A CN 110964309 A CN110964309 A CN 110964309A
Authority
CN
China
Prior art keywords
filler
weight
parts
modified
inorganic nano
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.)
Pending
Application number
CN201911270845.1A
Other languages
Chinese (zh)
Inventor
郭学章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Quanzhou Delandis Home Technology Co ltd
Original Assignee
Quanzhou Delandis Home Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Quanzhou Delandis Home Technology Co ltd filed Critical Quanzhou Delandis Home Technology Co ltd
Priority to CN201911270845.1A priority Critical patent/CN110964309A/en
Publication of CN110964309A publication Critical patent/CN110964309A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08J9/009—Use of pretreated compounding ingredients
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2421/00—Characterised by the use of unspecified rubbers
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a high-hardness sponge and a processing technology thereof, belonging to the field of sponge materials, and the technical scheme is characterized in that the raw materials comprise 14-24 parts of polyol, 4-14 parts of toluene diisocyanate, 0.12-0.2 part of foam stabilizer, 0.002-0.1 part of catalyst, 0.07-0.11 part of cyclopentane, 0.28-0.46 part of chain extender and 2.3-3.5 parts of filler according to parts by weight; the filler comprises a modified organic filler and a modified inorganic nano filler, and the weight ratio of the modified organic filler to the modified inorganic nano filler is 0.7-1.6; the effect of improving the hardness of the polyurethane elastomer is achieved.

Description

High-hardness sponge and processing technology thereof
Technical Field
The invention relates to the field of sponge materials, in particular to a high-hardness sponge and a processing technology thereof.
Background
The sponge is an elastic material made of foamed plastic polymer, and the sponge has the characteristics of heat preservation, heat insulation, sound absorption, shock absorption, flame retardance, good air permeability and the like, so the sponge relates to a plurality of industries such as the automobile industry, the battery industry, the cosmetic industry, the home furnishing industry and the like.
The sponge mattress is a modern common mattress, has good resilience characteristic, greatly reduces the necessity of turning over on the bed, further improves the sleeping quality of people, and has the characteristics of lightness, comfort and the like compared with mattresses made of other materials. However, the sponge mattress is soft, and cannot support the waist well when a person lies down, so that the lumbar muscle is in a tense state for a long time, particularly, the mattress is too soft and is not suitable for the growth of the skeleton of children and old people, and the old people lose most of the adjusting function due to the reduction of the elasticity of the muscle and ligament, and have adverse effects on intervertebral discs when sleeping on the soft mattress for a long time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-hardness sponge, and the effect of improving the hardness of a polyurethane elastomer is achieved.
The technical purpose of the invention is realized by the following technical scheme:
a high-hardness sponge comprises, by weight, 14-24 parts of polyol, 4-14 parts of toluene diisocyanate, 0.12-0.2 part of foam stabilizer, 0.002-0.1 part of catalyst, 0.07-0.11 part of cyclopentane, 0.28-0.46 part of chain extender and 2.3-3.5 parts of filler;
the filler comprises a modified organic filler and a modified inorganic nano filler, and the weight ratio of the modified organic filler to the modified inorganic nano filler is 0.7-1.6;
the modification method of the organic filler comprises the following steps: adding organic filler in parts by weight into a container, adding 25-35mL of distilled water, placing the container in a water bath at 28-34 ℃, adding a sodium hypochlorite solution with the weight being 2.2-2.5 times of the weight of the organic filler, stirring and reacting for more than 30min, cooling the mixed solution to 20-21 ℃ after the reaction is finished, centrifuging and washing, drying the obtained product at 75-85 ℃, and grinding the dried solid into powder to obtain the modified organic filler;
the modification method of the inorganic nano filler comprises the following steps: adding inorganic nano filler in parts by weight into a container, then adding 25-30mL of N-methyl pyrrolidone, then carrying out ultrasonic dispersion for 25-35min, then adding 4.6-8.6 parts of silane coupling agent in parts by weight, reacting for more than 2h, then carrying out centrifugal separation and precipitation, drying and grinding to obtain the modified inorganic nano filler.
By adopting the technical scheme, the organic filler contains a large amount of organic substances and organic functional groups, and the organic filler is added to change the viscosity of the matrix, help to improve the uniformity of cells in the matrix and improve the density of polyurethane, thereby improving the hardness of the polyurethane.
The inorganic nano-filler has small particle size, good dispersion performance in a polymer, large specific surface area, more surface atoms and unsaturated surface atoms, so that the activity of the inorganic nano-particles is high, and the inorganic nano-particles are combined with other atoms after being modified, so that strong acting force exists between the nano-particles and polymer molecular chains, and the formed polyurethane nano-composite material has excellent mechanical property.
The invention is further set that the raw materials comprise 16 to 22 portions of polyatomic alcohol, 6 to 12 portions of toluene diisocyanate, 0.14 to 0.18 portion of foam stabilizer, 0.004 to 0.008 portion of catalyst, 0.08 to 0.1 portion of cyclopentane, 0.31 to 0.42 portion of chain extender and 2.6 to 3.4 portions of filler according to the weight portion; the filler comprises modified organic filler and modified inorganic nano filler, and the weight ratio of the modified organic filler to the modified inorganic nano filler is 0.9-1.3.
The invention further provides that the polyhydric alcohol comprises polyoxypropylene ether diol and polycaprolactone diol, and the weight ratio of the polyoxypropylene ether diol to the polycaprolactone diol is (0.8-1.2) to (1.2-1.5).
By adopting the technical scheme, the molecular chain of the polycaprolactone diol contains ester bonds with higher bond energy, so that the strength is high, the heat-resistant effect is good, and the molecular chain motion barrier of the polyoxypropylene ether diol in the main chain is low, the flexibility is good, and the low-temperature performance is good.
The invention is further configured such that the foam stabilizer comprises silicone oil.
Through adopting above-mentioned technical scheme, the addition of silicone oil, can effectively reduce the surface tension of foam, make the inside and outside both sides pressure of bubble wall reach balance, prevent that the base member from producing the bubble phenomenon of collapsing, simultaneously can also reduce gas diffusion, stabilize the cell structure, make the even foam material of bubble, the addition of silicone oil simultaneously, can also increase the viscosity between the material, improve the toughness of bubble wall, increase the intensity of bubble wall, thereby reduce the impurity in the system as far as possible, avoid producing local bubble phenomenon of collapsing, but when the volume of silicone oil adds too much, can make the further attenuate of bubble pore wall, the intensity of bubble wall also can further reduction, thereby the phenomenon of easy bubble of collapsing, the intensity and the hardness that lead to polyurethane all can reduce.
The invention further provides that the catalyst comprises organotin and potassium octoate, and the weight ratio of the organotin to the potassium octoate is (0.6-0.9): (1.0-1.2).
By adopting the technical scheme, the catalyst plays an important role in the foaming reaction, and not only controls the chain extension reaction (between NCO-OH) and the foaming reaction (NCO-H)2O) balance between the two, and can also make the system reach ideal hairThe foam and the curing time enable the foam to reach the optimal rising height, and the foam does not collapse or shrink, and has excellent mechanical and physical properties, the foam collapse phenomenon easily occurs when the foam is foamed too fast, the foam volume is heavy or the foam shrinks and the like easily occurs when the foam is cured too fast, and even the performance of the product is influenced.
Organic tin can coordinate with isocyanate to polarize-NCO, so that positively charged carbon atoms in isocyanate molecules are more active and are more easily attacked by hydroxyl at the end of polyol polymer, and the catalytic activity is improved.
The potassium octoate has high catalytic activity, is not easy to hydrolyze, has good chemical stability, does not inactivate in the reaction process of the polyol and the toluene diisocyanate, has double functions of foaming and gelling, and is matched with the chain extender to promote the growth and crosslinking reaction of an NCO-OH chain. After the organic tin is matched with the potassium octoate for use, the foaming and curing time of a reaction system is effectively changed, and the strength and the hardness of a polyurethane product are improved.
The organic tin catalyst and the tertiary amine catalyst have better coordination effect when used together, and the foaming and curing time of the reaction system can be changed by adjusting the proportion of the organic tin catalyst and the tertiary amine catalyst.
The invention further provides that the organotin comprises one or both of dibutyltin dilaurate and stannous octoate.
The invention further provides that the organic filler comprises one or two of rubber powder and lignin.
By adopting the technical scheme, the rubber powder is powder particles prepared by crushing waste tires, the rubber powder contains a large amount of organic matters, but in the using process of the tires, due to the aging of the tires and the deposition of impurities on the surfaces, the rubber powder has poor compatibility with polyhydric alcohol and toluene diisocyanate when being directly added, so that the rubber powder is easy to agglomerate in a matrix, when the waste rubber powder is oxidized, active groups such as double bonds, methylene and the like on the surface of the rubber powder are oxidized into hydroxyl, the polarity and the reaction activity of the surface of the rubber powder are increased, the compatibility between the rubber powder and the polyhydric alcohol and the toluene diisocyanate is increased, and meanwhile, the hydroxyl generated on the surface of the rubber powder can also react with the toluene diisocyanate.
The lignin contains a plurality of functional groups such as phenolic hydroxyl, alcoholic hydroxyl, methoxyl, carbonyl, carboxyl and the like, so the lignin can generate a plurality of chemical reactions, but because the reactivity of each functional group in the lignin is insufficient, the compatibility of the lignin and a polyurethane matrix can be improved after the lignin is modified by sodium hypochlorite, meanwhile, the lignin contains alcoholic hydroxyl which can react with isocyanate to form a chemical bond, and simultaneously, the size of cells in the matrix is gradually reduced and tends to be consistent.
Benzene rings contained in the lignin have certain rigidity and can increase the density of foam, thereby being beneficial to improving the hardness of polyurethane
The invention further provides that the inorganic nano-filler comprises one or more of nano calcium carbonate, nano silicon dioxide and nano iron oxide.
The invention further provides that the chain extender comprises 1, 4-butanediol and 3,3 '-dichloro-4, 4-diaminodiphenylmethane, wherein the weight ratio of 1, 4-butanediol to 3,3' -dichloro-4, 4-diaminodiphenylmethane is (0.7-1.1): 1.2-1.5.
By adopting the technical scheme, the 1, 4-butanediol and the 3,3' -dichloro-4, 4-aminodiphenylmethane are matched for use, so that the polyurethane has excellent toughness and hardness, the foam structure and the aperture ratio can be adjusted, the polyurethane product is ensured to have certain resilience and excellent mechanical property, the component viscosity of the raw materials can be reduced, and the compatibility of the components among the raw materials can be improved.
Object two of the present invention: the processing technology of the high-hardness sponge comprises the following steps:
s1: adding polyol in parts by weight into a container, vacuumizing at the temperature of 100-120 ℃ and under the pressure of-0.1 MPa until no bubbles escape from the system, and then cooling to 50-65 ℃;
s2: adding toluene diisocyanate and a filler in parts by weight into the obtained product of the step S1, and reacting for more than 2 hours;
s3: adding a foam stabilizer, a catalyst, cyclopentane and a chain extender in parts by weight into the product obtained in the step S2, heating to 90-120 ℃, and reacting under the condition of-0.1 MPa until no bubbles are generated;
s4: and (4) stirring the obtained product of the step S3, pouring the stirred product into a mold, curing the product for 20-40 min at the temperature of 20-22 ℃, demolding, and drying the demolded product for more than 4h at the temperature of 65-75 ℃ to obtain the high-hardness sponge.
Through adopting above-mentioned technical scheme, carry out the evacuation to the polyol, can effectively reduce the influence of the content of moisture in the polyol to polyurethane, add toluene diisocyanate and filler afterwards, help filler to diffuse evenly in polyol, toluene diisocyanate, afterwards under the foaming effect of cyclopentane, in the filler fills the base member to play certain supporting role to the cell wall, improve polyurethane's intensity.
In conclusion, the invention has the following beneficial effects:
1. the addition of the modified organic filler and the modified inorganic filler can effectively change the viscosity of the polymer matrix, thereby effectively improving the uniformity of foam pores in the matrix, improving the density and mechanical properties of polyurethane and ensuring that the polyurethane has excellent hardness;
2. the synergistic use of the two catalysts of organotin and potassium octoate enables the polyurethane matrix to achieve ideal foaming and curing, enables the foam to achieve the optimal rise height, and enables the foam not to collapse and shrink, so that the polyurethane product has excellent mechanical and physical properties.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A high-hardness sponge comprises 14 parts of polyol, 4 parts of toluene diisocyanate, 0.12 part of silicone oil, 0.002 part of catalyst, 0.07 part of cyclopentane, 0.28 part of chain extender and 2.3 parts of filler;
the polyol comprises polyoxypropylene ether glycol and polycaprolactone glycol, and the weight ratio of the polyoxypropylene ether glycol to the polycaprolactone glycol is 0.8: 1.2;
the catalyst comprises stannous octoate and potassium octoate, wherein the weight ratio of the stannous octoate to the potassium octoate is 0.6: 1.0;
the chain extender comprises 1, 4-butanediol and 3,3 '-dichloro-4, 4-diaminodiphenylmethane, wherein the weight ratio of the 1, 4-butanediol to the 3,3' -dichloro-4, 4-diaminodiphenylmethane is 0.7: 1.2;
the filler comprises modified rubber powder and modified nano calcium carbonate, the weight ratio of the modified rubber powder to the modified nano calcium carbonate is 0.7, namely 0.95 part of the modified rubber powder and 1.35 parts of the modified nano calcium carbonate;
the modification method of the organic filler comprises the following steps: adding an organic filler in parts by weight into a container, adding 25mL of distilled water, placing the container in a water bath at 28 ℃, adding a sodium hypochlorite solution with the weight being 2.2 times of the weight of the organic filler, stirring and reacting for more than 30min, cooling the mixed solution to 20 ℃ after the reaction is finished, centrifuging and washing, drying the obtained product at 75 ℃, and grinding the dried solid into powder to obtain the modified organic filler;
the modification method of the inorganic nano filler comprises the following steps: adding inorganic nano filler in parts by weight into a container, then adding 25mL of N-methyl pyrrolidone, then performing ultrasonic dispersion for 25min, then adding 4.6 parts of silane coupling agent in parts by weight, reacting for more than 2h, performing centrifugal separation and precipitation, and drying and grinding to obtain modified inorganic nano filler;
a processing technology of high-hardness sponge comprises the following steps:
s1: adding polyol in parts by weight into a container, vacuumizing at 100 ℃ and under the pressure of-0.1 MPa until no bubbles escape from the system, and then cooling to 50 ℃;
s2: adding toluene diisocyanate and a filler in parts by weight into the obtained product of the step S1, and reacting for more than 2 hours;
s3: adding silicone oil, a catalyst, cyclopentane and a chain extender in parts by weight into the product obtained in the step S2, heating to 90 ℃, and reacting under the condition of-0.1 MPa until no bubbles are generated;
s4: and (4) stirring the obtained product of the step S3, pouring the stirred product into a mold, curing the product for 20min at the temperature of 20 ℃, demolding, and drying the demolded product for more than 4h at the temperature of 65 ℃ to obtain the high-hardness sponge.
Example 2
A high-hardness sponge comprises, by weight, 16 parts of polyol, 6 parts of toluene diisocyanate, 0.14 part of a foam stabilizer, 0.004 part of a catalyst, 0.08 part of cyclopentane, 0.31 part of a chain extender and 2.6 parts of a filler; the polyol comprises polyoxypropylene ether glycol and polycaprolactone glycol, and the weight ratio of the polyoxypropylene ether glycol to the polycaprolactone glycol is 0.9: 1.3;
the catalyst comprises stannous octoate and potassium octoate, wherein the weight ratio of the stannous octoate to the potassium octoate is 0.6: 1.0;
the chain extender comprises 1, 4-butanediol and 3,3 '-dichloro-4, 4-diaminodiphenylmethane, wherein the weight ratio of the 1, 4-butanediol to the 3,3' -dichloro-4, 4-diaminodiphenylmethane is 0.8: 1.3;
the filler comprises modified rubber powder and modified nano calcium carbonate, wherein the weight ratio of the modified rubber powder to the modified nano calcium carbonate is 0.9, namely 1.24 parts of the modified rubber powder and 1.36 parts of the modified nano calcium carbonate;
the modification method of the organic filler comprises the following steps: adding an organic filler in parts by weight into a container, adding 28mL of distilled water, placing the container in a water bath at 30 ℃, adding a sodium hypochlorite solution with the weight being 2.2 times of the weight of the organic filler, stirring and reacting for more than 30min, cooling the mixed solution to 20 ℃ after the reaction is finished, centrifuging and washing, drying the obtained product at 78 ℃, and grinding the dried solid into powder to obtain the modified organic filler;
the modification method of the inorganic nano filler comprises the following steps: adding inorganic nano filler in parts by weight into a container, then adding 26mL of N-methyl pyrrolidone, then performing ultrasonic dispersion for 25min, then adding 5.6 parts of silane coupling agent in parts by weight, reacting for more than 2h, performing centrifugal separation and precipitation, and drying and grinding to obtain modified inorganic nano filler;
a processing technology of high-hardness sponge comprises the following steps:
s1: adding polyol in parts by weight into a container, vacuumizing at 105 ℃ under the pressure of-0.1 MPa until no bubbles escape from the system, and then cooling to 58 ℃;
s2: adding toluene diisocyanate and a filler in parts by weight into the obtained product of the step S1, and reacting for more than 2 hours;
s3: adding silicone oil, a catalyst, cyclopentane and a chain extender in parts by weight into the product obtained in the step S2, heating to 100 ℃, and reacting under the condition of-0.1 MPa until no bubbles are generated;
s4: and (4) stirring the obtained product of the step S3, pouring the stirred product into a mold, curing the product for 25min at the temperature of 20 ℃, demolding, and drying the demolded product for more than 4h at the temperature of 68 ℃ to obtain the high-hardness sponge.
Example 3
A high-hardness sponge comprises, by weight, 19 parts of polyol, 9 parts of toluene diisocyanate, 0.16 part of a foam stabilizer, 0.051 part of a catalyst, 0.09 part of cyclopentane, 0.37 part of a chain extender and 2.9 parts of a filler; the polyol comprises polyoxypropylene ether glycol and polycaprolactone glycol, and the weight ratio of the polyoxypropylene ether glycol to the polycaprolactone glycol is 1.0: 1.4;
the catalyst comprises stannous octoate and potassium octoate, wherein the weight ratio of the stannous octoate to the potassium octoate is 0.8: 1.1;
the chain extender comprises 1, 4-butanediol and 3,3 '-dichloro-4, 4-diaminodiphenylmethane, wherein the weight ratio of the 1, 4-butanediol to the 3,3' -dichloro-4, 4-diaminodiphenylmethane is 0.9: 1.3;
the filler comprises modified rubber powder and modified nano calcium carbonate, wherein the weight ratio of the modified rubber powder to the modified nano calcium carbonate is 1.1, namely 1.52 parts of the modified rubber powder and 1.38 parts of the modified nano calcium carbonate;
the modification method of the organic filler comprises the following steps: adding organic filler in parts by weight into a container, adding 30mL of distilled water, placing the container in a water bath at 31 ℃, adding a sodium hypochlorite solution with the weight being 2.3 times of the weight of the organic filler, stirring and reacting for more than 30min, cooling the mixed solution to 20 ℃ after the reaction is finished, centrifuging and washing, drying the obtained product at 80 ℃, and grinding the dried solid into powder to obtain the modified organic filler;
the modification method of the inorganic nano filler comprises the following steps: adding inorganic nano filler in parts by weight into a container, then adding 28mL of N-methyl pyrrolidone, then performing ultrasonic dispersion for 30min, then adding 6.6 parts of silane coupling agent in parts by weight, reacting for more than 2h, performing centrifugal separation and precipitation, and drying and grinding to obtain modified inorganic nano filler;
a processing technology of high-hardness sponge comprises the following steps:
s1: adding polyol in parts by weight into a container, vacuumizing at the temperature of 110 ℃ and under the pressure of-0.1 MPa until no bubbles escape from the system, and then cooling to 58 ℃;
s2: adding toluene diisocyanate and a filler in parts by weight into the obtained product of the step S1, and reacting for more than 2 hours;
s3: adding a foam stabilizer, a catalyst, cyclopentane and a chain extender in parts by weight into the product obtained in the step S2, heating to 105 ℃, and reacting under the condition of-0.1 MPa until no bubbles are generated;
s4: and (4) stirring the obtained product of the step S3, pouring the stirred product into a mold, curing the product for 30min at the temperature of 21 ℃, demolding, and drying the demolded product for more than 4h at the temperature of 70 ℃ to obtain the high-hardness sponge.
Example 4
A high-hardness sponge comprises, by weight, 22 parts of polyol, 12 parts of toluene diisocyanate, 0.18 part of a foam stabilizer, 0.008 part of a catalyst, 0.1 part of cyclopentane, 0.42 part of a chain extender and 3.4 parts of a filler; the polyol comprises polyoxypropylene ether glycol and polycaprolactone glycol, and the weight ratio of the polyoxypropylene ether glycol to the polycaprolactone glycol is 1.1: 1.4;
the catalyst comprises stannous octoate and potassium octoate, wherein the weight ratio of the stannous octoate to the potassium octoate is 0.9: 1.2;
the chain extender comprises 1, 4-butanediol and 3,3 '-dichloro-4, 4-diaminodiphenylmethane, wherein the weight ratio of the 1, 4-butanediol to the 3,3' -dichloro-4, 4-diaminodiphenylmethane is 1.0: 1.4;
the filler comprises modified rubber powder and modified nano calcium carbonate, wherein the weight ratio of the modified rubber powder to the modified nano calcium carbonate is 1.3, namely 1.93 parts of the modified rubber powder and 1.47 parts of the modified nano calcium carbonate;
the modification method of the organic filler comprises the following steps: adding an organic filler in parts by weight into a container, adding 32mL of distilled water, placing the container in a water bath at 33 ℃, adding a sodium hypochlorite solution with the weight being 2.5 times of the weight of the organic filler, stirring and reacting for more than 30min, cooling the mixed solution to 21 ℃ after the reaction is finished, centrifuging and washing, drying the obtained product at 82 ℃, and grinding the dried solid into powder to obtain the modified organic filler;
the modification method of the inorganic nano filler comprises the following steps: adding inorganic nano filler in parts by weight into a container, then adding 28mL of N-methyl pyrrolidone, then performing ultrasonic dispersion for 32min, then adding 7.6 parts of silane coupling agent in parts by weight, reacting for more than 2h, performing centrifugal separation and precipitation, and drying and grinding to obtain modified inorganic nano filler;
a processing technology of high-hardness sponge comprises the following steps:
s1: adding polyol in parts by weight into a container, vacuumizing at the temperature of 115 ℃ and under the pressure of-0.1 MPa until no bubbles escape from the system, and then cooling to 61 ℃;
s2: adding toluene diisocyanate and a filler in parts by weight into the obtained product of the step S1, and reacting for more than 2 hours;
s3: adding a foam stabilizer, a catalyst, cyclopentane and a chain extender in parts by weight into the product obtained in the step S2, heating to 115 ℃, and reacting under the condition of-0.1 MPa until no bubbles are generated;
s4: and (4) stirring the obtained product of the step S3, pouring the stirred product into a mold, curing the product at 22 ℃ for 35min, demolding, and drying the demolded product at 72 ℃ for more than 4h to obtain the high-hardness sponge.
Example 5
A high-hardness sponge comprises, by weight, 24 parts of polyol, 14 parts of toluene diisocyanate, 0.2 part of a foam stabilizer, 0.1 part of a catalyst, 0.11 part of cyclopentane, 0.46 part of a chain extender and 3.5 parts of a filler; the polyol comprises polyoxypropylene ether glycol and polycaprolactone glycol, and the weight ratio of the polyoxypropylene ether glycol to the polycaprolactone glycol is 1.2: 1.5;
the catalyst comprises stannous octoate and potassium octoate, wherein the weight ratio of the stannous octoate to the potassium octoate is 0.9: 1.2;
the chain extender comprises 1, 4-butanediol and 3,3 '-dichloro-4, 4-diaminodiphenylmethane, wherein the weight ratio of the 1, 4-butanediol to the 3,3' -dichloro-4, 4-diaminodiphenylmethane is 1.1: 1.5;
the filler comprises modified rubber powder and modified nano calcium carbonate, wherein the weight ratio of the modified rubber powder to the modified nano calcium carbonate is 1.6, namely 2.16 parts of the modified rubber powder and 1.34 parts of the modified nano calcium carbonate;
the modification method of the organic filler comprises the following steps: adding an organic filler in parts by weight into a container, adding 35mL of distilled water, placing the container in a water bath at 34 ℃, adding a sodium hypochlorite solution with the weight 2.5 times that of the organic filler, stirring and reacting for more than 30min, cooling the mixed solution to 21 ℃ after the reaction is finished, centrifuging and washing, drying the obtained product at 85 ℃, and grinding the dried solid into powder to obtain the modified organic filler;
the modification method of the inorganic nano filler comprises the following steps: adding inorganic nano filler in parts by weight into a container, then adding 30mL of N-methyl pyrrolidone, then performing ultrasonic dispersion for 35min, then adding 8.6 parts of silane coupling agent in parts by weight, reacting for more than 2h, performing centrifugal separation and precipitation, and drying and grinding to obtain modified inorganic nano filler;
a processing technology of high-hardness sponge comprises the following steps:
s1: adding polyol in parts by weight into a container, vacuumizing at the temperature of 120 ℃ and under the pressure of-0.1 MPa until no bubbles escape from the system, and then cooling to 65 ℃;
s2: adding toluene diisocyanate and a filler in parts by weight into the obtained product of the step S1, and reacting for more than 2 hours;
s3: adding a foam stabilizer, a catalyst, cyclopentane and a chain extender in parts by weight into the product obtained in the step S2, heating to 120 ℃, and reacting under the condition of-0.1 MPa until no bubbles are generated;
s4: and (4) stirring the obtained product of the step S3, pouring the stirred product into a mold, curing the product for 40min at the temperature of 22 ℃, demolding, and drying the demolded product for more than 4h at the temperature of 75 ℃ to obtain the high-hardness sponge.
Example 6
A high-hardness polyurethane which differs from example 3 in that the modified organic filler is modified with an equivalent amount of modified lignin in place of the modified rubber crumb.
Example 7
A high hardness polyurethane which differs from that of example 3 in that the stannous octoate was replaced with the same amount of dibutyltin dilaurate.
Example 8
A high-hardness polyurethane which is different from example 3 in that the same amount of modified nano-silica was used in place of the modified calcium carbonate.
Example 9
A high-hardness polyurethane which is different from that in example 3 in that the same amount of modified nano iron oxide was used in place of the modified calcium carbonate.
Example 10
The high-hardness polyurethane is different from the polyurethane in the embodiment 3 in that the modified inorganic nano filler comprises 0.46 part by weight of modified nano calcium carbonate, modified nano silica and modified nano iron oxide.
Example 11
A high-hardness polyurethane which is different from example 3 in that the modified organic filler comprises 0.76 parts by weight of modified rubber powder and modified lignin.
Comparative example 1
The difference from example 3 is that the modified rubber powder was replaced with an equal amount of rubber powder.
Comparative example 2
The difference from example 3 is that the modified nano calcium carbonate is replaced by the same amount of nano calcium carbonate.
Comparative example 3
The difference from example 3 is that only 1, 4-butanediol was used as the chain extender.
Comparative example 4
The difference from example 3 is that only 3,3' -dichloro-4, 4-aminodiphenylmethane was used as the chain extender.
Comparative example 5
The difference from example 3 is that the catalyst used was organotin only.
Comparative example 6
The difference from example 3 is that the catalyst used was only potassium octoate.
Comparative example 7
The difference from example 3 is that the weight part of the chain extender is 0.51 part.
Comparative example 8
The difference from example 3 is that the weight part of the chain extender is 0.2 part.
Comparative example 9
The difference from example 3 is that the weight part of the catalyst is 0.001 part.
Comparative example 10
The difference from example 3 is that the weight part of the catalyst is 0.15 part.
Performance detection
The polyurethane sponges prepared in examples 1 to 11 and comparative examples 1 to 10 were subjected to property tests, and the test results are shown in table 1. The hardness, indentation ratio, compression set, rebound resilience and tensile strength of the polyurethane sponge are tested according to the standard of GB/T10802-2006.
Figure BDA0002313052930000111
From the above table, it can be seen that:
in examples 1-5, the hardness, indentation ratio, tensile strength and density tended to increase and then decrease, and were all maximized in example 3, while the 75% compression set was maximized and the spring rate was minimized, but the 75% compression set and spring rate were within the standard requirements, indicating that the formulation in example 3 was more conducive to improving the hardness of the polyurethane sponge, and also could make the polyurethane sponge have a certain elasticity, making the polyurethane sponge more comfortable when used as a mattress;
compared with the example 3, after the same amount of modified lignin replaces the modified rubber powder, the same amount of dibutyltin dilaurate replaces stannous octoate, the same amount of modified nano-silica replaces the modified calcium carbonate, and the same amount of modified nano-iron oxide replaces the modified calcium carbonate, the performances of the examples 6 to 9 are basically the same as those of the example 3, which shows that the modified lignin, the dibutyltin dilaurate, the modified nano-silica and the modified nano-iron oxide can also achieve basically the same effects;
compared with the example 3, when the modified inorganic filler adopts the modified nano calcium carbonate, the modified nano silica and the modified nano iron oxide, the hardness, the indentation ratio, the tensile strength and the density in the example 10 are obviously improved compared with the example 3, meanwhile, the compression set of 75 percent is increased, the rebound rate is reduced, but the compression set of 75 percent is increased, and the rebound rate is in the standard requirement range; when the modified rubber powder and the modified lignin are used simultaneously, the hardness, the indentation ratio, the tensile strength and the density in the embodiment 11 are obviously improved compared with those in the embodiment 3, the 75% compression set is correspondingly increased, and the rebound resilience is correspondingly reduced, but all within the standard, so that the hardness of the polyurethane sponge can be effectively improved when the modified nano calcium carbonate, the modified nano silica and the modified nano iron oxide are used simultaneously, and the polyurethane sponge has certain elasticity; when the modified rubber powder and the modified lignin are used, the hardness of the polyurethane sponge is effectively improved, and meanwhile, the polyurethane sponge keeps certain elasticity, so that the use comfort is improved;
comparative examples 1-2 compared to example 3, when both the rubber powder and the nano calcium carbonate were not modified, the hardness and density of the polyurethane sponge were decreased, but the elasticity was increased, making the polyurethane mattress softer;
compared with the example 3, when only one of the chain extenders is adopted, the hardness and the density of the polyurethane sponge are reduced, which shows that the polyurethane sponge has proper crosslinking degree and the comfort of the polyurethane mattress is improved by the matching use of the chain extender;
compared with the embodiment 3, in the embodiments 5 to 6, when the catalyst only adopts organic tin or only adopts potassium octoate, the hardness of the polyurethane sponge is correspondingly reduced, which indicates that the catalyst is used in combination, the crosslinking degree of the polyurethane is effectively controlled, the hardness of the polyurethane mattress is improved, and meanwhile, the polyurethane mattress has certain elasticity and the use comfort is improved;
in examples 7 to 10, compared with example 3, when the amounts of the chain extender and the catalyst are beyond the use range, the hardness of the polyurethane sponge is also obviously reduced, which shows that the range in the invention can effectively improve the hardness of the polyurethane sponge.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (10)

1. A high hardness sponge, characterized in that: the raw materials comprise 14 to 24 portions of polyol, 4 to 14 portions of toluene diisocyanate, 0.12 to 0.2 portion of foam stabilizer, 0.002 to 0.1 portion of catalyst, 0.07 to 0.11 portion of cyclopentane, 0.28 to 0.46 portion of chain extender and 2.3 to 3.5 portions of filler according to the weight portion;
the filler comprises a modified organic filler and a modified inorganic nano filler, and the weight ratio of the modified organic filler to the modified inorganic nano filler is 0.7-1.6;
the modification method of the organic filler comprises the following steps: adding organic filler in parts by weight into a container, adding 25-35mL of distilled water, placing the container in a water bath at 28-34 ℃, adding a sodium hypochlorite solution with the weight being 2.2-2.5 times of the weight of the organic filler, stirring and reacting for more than 30min, cooling the mixed solution to 20-21 ℃ after the reaction is finished, centrifuging and washing, drying the obtained product at 75-85 ℃, and grinding the dried solid into powder to obtain the modified organic filler;
the modification method of the inorganic nano filler comprises the following steps: adding inorganic nano filler in parts by weight into a container, then adding 25-30mL of N-methyl pyrrolidone, then carrying out ultrasonic dispersion for 25-35min, then adding 4.6-8.6 parts of silane coupling agent in parts by weight, reacting for more than 2h, then carrying out centrifugal separation and precipitation, drying and grinding to obtain the modified inorganic nano filler.
2. The high hardness sponge according to claim 1, wherein: the raw materials comprise 16 to 22 portions of polyatomic alcohol, 6 to 12 portions of toluene diisocyanate, 0.14 to 0.18 portion of foam stabilizer, 0.004 to 0.008 portion of catalyst, 0.08 to 0.1 portion of cyclopentane, 0.31 to 0.42 portion of chain extender and 2.6 to 3.4 portions of filler according to the weight portion; the filler comprises modified organic filler and modified inorganic nano filler, and the weight ratio of the modified organic filler to the modified inorganic nano filler is 0.9-1.3.
3. The high hardness sponge according to claim 1, wherein: the polyol comprises polyoxypropylene ether diol and polycaprolactone diol, and the weight ratio of the polyoxypropylene ether diol to the polycaprolactone diol is (0.8-1.2) to (1.2-1.5).
4. The high hardness sponge according to claim 1, wherein: the foam stabilizer comprises silicone oil.
5. The high hardness sponge according to claim 1, wherein: the catalyst comprises organotin and potassium octoate, the weight ratio of the organotin to the potassium octoate is (0.6-0.9): (1.0-1.2).
6. The high hardness sponge according to claim 5, wherein: the organic tin comprises one or two of dibutyltin dilaurate and stannous octoate.
7. The high hardness sponge according to claim 1, wherein: the organic filler comprises one or two of rubber powder and lignin.
8. The high hardness sponge according to claim 1, wherein: the inorganic nano filler comprises one or more of nano calcium carbonate, nano silicon dioxide and nano iron oxide.
9. The high hardness sponge according to claim 1, wherein: the chain extender comprises 1, 4-butanediol and 3,3 '-dichloro-4, 4-diaminodiphenylmethane, wherein the weight ratio of the 1, 4-butanediol to the 3,3' -dichloro-4, 4-diaminodiphenylmethane is (0.7-1.1) to (1.2-1.5).
10. A process for manufacturing a high hardness sponge according to any one of claims 1 to 9, comprising the steps of:
s1: adding polyol in parts by weight into a container, vacuumizing at the temperature of 100-120 ℃ and under the pressure of-0.1 MPa until no bubbles escape from the system, and then cooling to 50-65 ℃;
s2: adding toluene diisocyanate and a filler in parts by weight into the obtained product of the step S1, and reacting for more than 2 hours;
s3: adding a foam stabilizer, a catalyst, cyclopentane and a chain extender in parts by weight into the product obtained in the step S2, heating to 90-120 ℃, and reacting under the condition of-0.1 MPa until no bubbles are generated;
s4: and (4) stirring the obtained product of the step S3, pouring the stirred product into a mold, curing the product for 20-40 min at the temperature of 20-22 ℃, demolding, and drying the demolded product for more than 4h at the temperature of 65-75 ℃ to obtain the high-hardness sponge.
CN201911270845.1A 2019-12-11 2019-12-11 High-hardness sponge and processing technology thereof Pending CN110964309A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911270845.1A CN110964309A (en) 2019-12-11 2019-12-11 High-hardness sponge and processing technology thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911270845.1A CN110964309A (en) 2019-12-11 2019-12-11 High-hardness sponge and processing technology thereof

Publications (1)

Publication Number Publication Date
CN110964309A true CN110964309A (en) 2020-04-07

Family

ID=70033838

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911270845.1A Pending CN110964309A (en) 2019-12-11 2019-12-11 High-hardness sponge and processing technology thereof

Country Status (1)

Country Link
CN (1) CN110964309A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111941632A (en) * 2020-08-25 2020-11-17 重庆君秀科技有限公司 Energy-saving self-heat-insulation prefabricated wall body for building

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210066A (en) * 2006-12-30 2008-07-02 比亚迪股份有限公司 Entire polyurethane foam composition
CN101864164A (en) * 2010-06-24 2010-10-20 东莞市丞冠橡塑制品有限公司 Production method of polyurethane insole material
CN102391639A (en) * 2011-09-30 2012-03-28 常熟市星源金属涂层厂 Polyurethane and rubber foamed compound material and preparation method thereof
CN103273711A (en) * 2013-06-09 2013-09-04 山东普兰特板业有限公司 Silicon dioxide modified polyurethane sandwich panel for heat preservation of refrigeration storage
CN105131231A (en) * 2015-09-29 2015-12-09 东莞赛诺家居用品有限公司 Memory cotton
CN105131560A (en) * 2015-07-17 2015-12-09 济南骄泰信息技术有限公司 Modified lignin polyurethane and preparation method thereof
CN105504203A (en) * 2016-02-03 2016-04-20 广西吉顺能源科技有限公司 Polyurethane rigid foam
CN105693974A (en) * 2016-02-03 2016-06-22 广西吉顺能源科技有限公司 Solar polyurethane thermal insulation material
CN107722350A (en) * 2017-10-16 2018-02-23 南京大学 A kind of polyhydroxy silicon nitrogen type flame retardant and its preparation method and the application in anti-inflaming polyurethane hard foam material
CN108084394A (en) * 2017-12-25 2018-05-29 青岛科技大学 A kind of shape memory hard polyurethane foam medical splint material and preparation method thereof
CN108659194A (en) * 2018-04-26 2018-10-16 青岛海尔股份有限公司 A kind of polyurethane rigid foam plastic composite material and preparation method and purposes
EP3425187A1 (en) * 2017-07-07 2019-01-09 Covestro Deutschland AG Flame retardant insulation for internal combustion engines
CN109912963A (en) * 2019-03-23 2019-06-21 天津市海纳源科技有限公司 A kind of production method of waste old powder filled polyurethane plastics

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210066A (en) * 2006-12-30 2008-07-02 比亚迪股份有限公司 Entire polyurethane foam composition
CN101864164A (en) * 2010-06-24 2010-10-20 东莞市丞冠橡塑制品有限公司 Production method of polyurethane insole material
CN102391639A (en) * 2011-09-30 2012-03-28 常熟市星源金属涂层厂 Polyurethane and rubber foamed compound material and preparation method thereof
CN103273711A (en) * 2013-06-09 2013-09-04 山东普兰特板业有限公司 Silicon dioxide modified polyurethane sandwich panel for heat preservation of refrigeration storage
CN105131560A (en) * 2015-07-17 2015-12-09 济南骄泰信息技术有限公司 Modified lignin polyurethane and preparation method thereof
CN105131231A (en) * 2015-09-29 2015-12-09 东莞赛诺家居用品有限公司 Memory cotton
CN105504203A (en) * 2016-02-03 2016-04-20 广西吉顺能源科技有限公司 Polyurethane rigid foam
CN105693974A (en) * 2016-02-03 2016-06-22 广西吉顺能源科技有限公司 Solar polyurethane thermal insulation material
EP3425187A1 (en) * 2017-07-07 2019-01-09 Covestro Deutschland AG Flame retardant insulation for internal combustion engines
CN107722350A (en) * 2017-10-16 2018-02-23 南京大学 A kind of polyhydroxy silicon nitrogen type flame retardant and its preparation method and the application in anti-inflaming polyurethane hard foam material
CN108084394A (en) * 2017-12-25 2018-05-29 青岛科技大学 A kind of shape memory hard polyurethane foam medical splint material and preparation method thereof
CN108659194A (en) * 2018-04-26 2018-10-16 青岛海尔股份有限公司 A kind of polyurethane rigid foam plastic composite material and preparation method and purposes
CN109912963A (en) * 2019-03-23 2019-06-21 天津市海纳源科技有限公司 A kind of production method of waste old powder filled polyurethane plastics

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WANG RUIQI，等: "Preparation and Characterization of Rigid Polyurethane Foams with Different Loadings of Lignin-Derived Polycarboxylic Acids", 《INTERNATIONAL JOURNAL OF POLYMER SCIENCE》 *
牟东兰，等: "次氯酸钠对硫化橡胶粉表面的氧化改性研究", 《化学研究与应用》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111941632A (en) * 2020-08-25 2020-11-17 重庆君秀科技有限公司 Energy-saving self-heat-insulation prefabricated wall body for building
CN111941632B (en) * 2020-08-25 2022-08-26 郴州市长信住工科技有限公司 Energy-saving self-heat-insulation prefabricated wall body for building

Similar Documents

Publication Publication Date Title
CN107857865B (en) Full-water environment-friendly flame-retardant flatulence memory polyurethane foam for automobile seat and preparation method thereof
CN101205288B (en) Polyurethane foam compositions
CN101585901B (en) Polyurethane foam material and preparing method and application thereof
EP2331597B1 (en) Process for the preparation of flexible, resilient polyurethane foam and the resulting foam
WO2011132645A1 (en) Polyurethane foam for seat pad
SG193457A1 (en) Auto-crusting microporous elastomer composition foruse in polyurethane foam-filled tire
CN1961016A (en) Low-density polyurethane foam materials and their use in shoe soles
CN115124693B (en) Foaming polyurethane elastomer and preparation method and application thereof
CN110885417A (en) Compression-resistant low-density TDI (toluene diisocynate) type high-resilience foam sponge and preparation method thereof
AU689616B2 (en) Soft, low density flexible polyurethane foam
CN111548475B (en) Slow-rebound memory cotton and preparation method thereof
CN113105664B (en) Polyurethane foam stabilizer
JP2006342305A (en) Method for producing rigid polyurethane foam
CN105732935B (en) A kind of preparation method of microporous polyurethane elastomer
CN110964309A (en) High-hardness sponge and processing technology thereof
CN113061225B (en) Self-submersible polyurethane foam plastic and preparation method and application thereof
CN112457554A (en) Environment-friendly composite mattress containing bamboo fibers and preparation method thereof
CN110951241A (en) Lavender memory cotton and preparation method thereof
CN113292697A (en) Ultra-high density polyurethane soft foam and preparation method thereof
CN106608960B (en) Preparation method of polyurethane microporous elastomer
KR102500160B1 (en) Automotive seat pad having improved dynamic comfort, method for preparing the same and isocyanate prepolymer for preparing the same
CN112812268B (en) Low-temperature-resistant memory cotton for pillow and preparation method and application thereof
CN108314771B (en) High-elasticity antibacterial foamed polyurethane and preparation method and application thereof
CN112062927B (en) Polyurethane soft foam plastic and preparation method thereof
KR20110054365A (en) Composition of flexible polyurethane foam having antimicrobial durability and automobile seats having that

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20200407

RJ01 Rejection of invention patent application after publication