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CN108203885A - A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather - Google Patents

A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather Download PDF

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Publication number
CN108203885A
CN108203885A CN201711454409.0A CN201711454409A CN108203885A CN 108203885 A CN108203885 A CN 108203885A CN 201711454409 A CN201711454409 A CN 201711454409A CN 108203885 A CN108203885 A CN 108203885A
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synthetic leather
preparation
resistant
silicon materials
high strength
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庄加松
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Fengyang Jiasong New Material Technology Co Ltd
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Fengyang Jiasong New Material Technology Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/067—Flame resistant, fire resistant
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/108—Slipping, anti-blocking, low friction
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
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    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
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    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
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    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance
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    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of preparation methods of heat-resistant, high strength degree macromolecule silicon materials synthetic leather, include the following steps：（1）The preparation of organosiloxane monomer mixture,（2）Modified filler preparation,（3）Organic polysiloxane emulsion preparation,（4）It is prepared by finished product synthetic leather.The present invention has carried out the preparation method of macromolecule silicon materials synthetic leather special improvement processing, it is effectively improved using quality, final synthetic leather obtained has that very strong heatproof flame-retardant, anti-corrosion be ageing-resistant, wear-resisting wrinkle properties, good mechanical performance, service life is long, great application value.

Description

A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of system of heat-resistant, high strength degree macromolecule silicon materials synthetic leather Preparation Method.
Background technology
Synthetic leather is relative to " leather "（That is corium）For saying.Also referred to as artificial leather, synthetic leather.China for Synthetic leather has no standard saying, is generally divided into PVC synthetic leather, PU synthetic leather etc. according to the type of its surface resin.With skill The development of art, emerging a kind of macromolecule silicon materials synthetic leather now, be by macromolecule silicon materials and base fabric co-manufactured and Into a kind of new varieties synthetic leather, compared to common PVC synthetic leather, PU synthetic leather etc. have more feel elasticity and service life. But with the continuous promotion that people require synthesising leather performance, the intensity of the macromolecule silicon materials synthetic leather on existing market, The qualities such as heatproof, ageing-resistant can not meet the needs of user, and further improvement is needed to handle.
Invention content
The purpose of the present invention is being directed to the problem of existing, a kind of heat-resistant, high strength degree macromolecule silicon materials synthetic leather is provided Preparation method.
The present invention is achieved by the following technical solutions：
A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather, includes the following steps：
（1）Organosiloxane monomer mixture is prepared：
By cyclic siloxane monomer, function groups siloxanyl monomers and vinylsiloxane monomer correspondence according to weight ratio 65 ~ 70: 0.8~1.5:3 ~ 5, which carry out mixing, is put into agitator tank, and high-speed stirred obtains the mixing of organosiloxane monomer after handling 30 ~ 35min Object is spare；
（2）It is prepared by modified filler：
A. by cetyl dihydroxy ethyl amine oxide, nonylphenol polyoxyethylene ether and ethanol solution according to mass ratio 2:0.7：10~ 13 common mixing are put into reaction kettle, after being stirred continuously 18 ~ 22min of processing, then ammonium hydroxide are added dropwise into reaction kettle, are stirred continuously After handling 20 ~ 24min, then ethyl orthosilicate is added in into reaction kettle, it is standby to obtain mixture A after constantly 25 ~ 30min of supersound process With；
B. the modification mixed liquor of its gross mass 22 ~ 26% is added into the mixture A obtained by operation a, then heating keeps reaction kettle Interior temperature is 72 ~ 75 DEG C, and the pressure in reaction kettle is increased to 0.44 ~ 0.48MPa, and it is laggard to be stirred continuously 28 ~ 33min of processing Row filtering, finally by the filter residue of gained be put into drying box be dried 45 ~ 50min after take out modified filler is spare；Institute State material composition of the modified mixed liquor by following parts by weight：30 ~ 34 parts of chopped carbon fibers, 14 ~ 18 parts of nano-bentonite powder, 5 ~ 9 Part titanate coupling agent, 6 ~ 8 parts of calcium stearates, 4 ~ 7 parts of ethyl methacrylate, 4 ~ 6 parts of dimethyl carbonates, 3 ~ 6 parts of bacterium fibres Dimension element, 620 ~ 660 parts of water；
（3）Organic polysiloxane emulsion is prepared：
A. by step（1）The organosiloxane monomer mixture of gained is put into homogenizer, and high speed shear handles 10 ~ 15min, Then it puts into again in the aqueous solution dissolved with catalyst and emulsifier, it is 82 ~ 86 DEG C to keep whole temperature, is stirred continuously place It is spare that mixed liquid B is obtained after 5 ~ 8h of reason；The gross mass of the organosiloxane monomer mixture is the 30 ~ 35% of water quality, aqueous solution The dosage of middle catalyst is the 2 ~ 4% of organosiloxane monomer mixture gross mass, and the dosage of emulsifier is organosilicon in aqueous solution The 7 ~ 10% of oxygen alkane monomer mixture gross mass；
B. the pH value of the mixed liquid B obtained by operation a is adjusted to 10 ~ 11, then adds in initiator, crosslinking agent and step（2）System The modified filler obtained, it is 75 ~ 80 DEG C to keep whole temperature, and organic polysiloxane emulsion is taken out to obtain after being stirred continuously 6 ~ 8h of processing It is spare；The dosage of the initiator is the 0.4 ~ 0.6% of mixed liquid B gross mass, and the dosage of the crosslinking agent is the total matter of mixed liquid B The 0.1 ~ 0.3% of amount, the dosage of the modified filler is the 7 ~ 9% of mixed liquid B gross mass；
（4）It is prepared by finished product synthetic leather：
By step（3）Organic polysiloxane emulsion obtained coats curing and synthesis is got product after in base fabric according to a conventional method Leather.
Further, step（1）Described in cyclic siloxane monomer for hexamethyl cyclotrisiloxane, four silicon of prestox ring Any one in oxygen alkane, decamethylcyclopentaandoxane, the function groups siloxanyl monomers are methyltriethoxysilane, Any one in vinyltrimethoxysilane, phenyl triethoxysilane, the vinylsiloxane monomer are ethylene Any one in ethyl triethoxy silicane alkane, divinyl diethoxy silane, vinyl methyl diethoxy silane.
Further, step（2）The volume fraction for operating ethyl alcohol in the ethanol solution described in a is 56 ~ 58%, described The dripping quantity of ammonium hydroxide is the 18 ~ 22% of ethanol solution gross mass, and the additive amount of the ethyl orthosilicate is ethanol solution gross mass 5.2 ~ 5.4 times.
Further, step（2）The frequency for operating the supersound process described in a is 88 ~ 94kHz.
Further, step（2）Temperature when operating the drying process described in b in control drying box is 88 ~ 92 DEG C.
Further, step（3）Operate a described in high speed shear processing when shearing rotating speed for 10000 ~ 12000 turns/ Minute.
Further, step（3）The catalyst operated described in a is pyrovinic acid, in ethylsulfonic acid, acid dimethyl Any one, the emulsifier is polyglyceryl fatty acid ester, methyl glycol fatty acid ester, in Exxal 12 polyoxyethylene ether Any one.
Further, step（3）The initiator operated described in b is tert-butyl hydroperoxide, lauroyl peroxide, peroxide Change any one in diisopropylbenzene (DIPB), the crosslinking agent is Malaysia allyl propionate, diethyleneglycol dimethacrylate, diformazan Any one in base propylene acid propylene glycol ester.
Further, step（4）Described in base fabric be looped fabric, woven fabric, any one in non-woven fabrics.
The present invention has carried out the preparation method of macromolecule silicon materials synthetic leather special improvement processing, especially to wherein Organic polysiloxane emulsion improved, its constituent is optimized, wherein cyclic siloxane monomer, more has been selected in collocation Three kinds of monomer components of functional group siloxanyl monomers and vinylsiloxane monomer are polymerize, improve bulk polymerization efficiency, Intensity quality, and it is added to a kind of special modified filler ingredient again, it is using ethyl orthosilicate as silicon source, ethanol solution is Solvent, ammonium hydroxide are catalyst, and modified mixed liquor is modifying agent, cetyl dihydroxy ethyl amine oxide and nonylphenol polyoxyethylene ether It is common manufactured with porous, pogoniasis shape structure silica filler for activating agent and template, it is modified being chopped in mixed liquor Carbon fiber, nano-bentonite powder can enhance the heatproof flame-retardant of silica, and chopped carbon fiber can promote macromolecule silicon materials Bonding strength between being organized everywhere in matrix, improves whole mechanical quality, and nano-bentonite powder has very big specific surface Product and adsorption capacity, the polymerization for monomer provide attachment site, play the role of nucleation enhancing, while its special lamella Structure can promote the smooth property and hand feeling quality on synthetic leather surface again, this two kinds of ingredients silica generate during, Effective grafting is secured within, and modified effect is good, and stability is high, remaining ingredient in modified mixed liquor effectively improves two The surface reaction activity of silica and the compatible binding characteristic between macromolecule silicon materials matrix composition, enhance its filling Use quality.
The present invention has the following advantages compared with prior art：
The present invention has carried out the preparation method of macromolecule silicon materials synthetic leather special improvement processing, effectively improves its use Quality, final obtained synthetic leather have that very strong heatproof flame-retardant, anti-corrosion be ageing-resistant, wear-resisting wrinkle properties, good mechanical performance, Service life is long, great application value.
Specific embodiment
Embodiment 1
A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather, includes the following steps：
（1）Organosiloxane monomer mixture is prepared：
By cyclic siloxane monomer, function groups siloxanyl monomers and vinylsiloxane monomer correspondence according to weight ratio 65: 0.8:3, which carry out mixing, is put into agitator tank, and it is spare to obtain organosiloxane monomer mixture after high-speed stirred processing 30min；
（2）It is prepared by modified filler：
A. by cetyl dihydroxy ethyl amine oxide, nonylphenol polyoxyethylene ether and ethanol solution according to mass ratio 2:0.7：10 is common It is put into reaction kettle with mixing, after being stirred continuously processing 18min, then ammonium hydroxide is added dropwise into reaction kettle, is stirred continuously processing After 20min, then ethyl orthosilicate is added in into reaction kettle, it is spare to obtain mixture A after constantly supersound process 25min；
B. the modification mixed liquor of its gross mass 22% is added into the mixture A obtained by operation a, then heating is kept in reaction kettle Temperature for 72 DEG C, and the pressure in reaction kettle is increased into 0.44MPa, is filtered after being stirred continuously processing 28min, finally will The filter residue of gained be put into drying box be dried after 45min take out modified filler is spare；The modified mixed liquor is by such as The material composition of lower parts by weight：30 parts of chopped carbon fibers, 14 parts of nano-bentonite powder, 5 parts of titanate coupling agents, 6 parts of stearic acid Calcium, 4 parts of ethyl methacrylate, 4 parts of dimethyl carbonates, 3 parts of bacteria celluloses, 620 parts of water；
（3）Organic polysiloxane emulsion is prepared：
A. by step（1）The organosiloxane monomer mixture of gained is put into homogenizer, high speed shear processing 10min, so It puts into again in the aqueous solution dissolved with catalyst and emulsifier afterwards, it is 82 DEG C to keep whole temperature, is stirred continuously processing 5h It is spare that mixed liquid B is obtained afterwards；The gross mass of the organosiloxane monomer mixture is the 30% of water quality, catalyst in aqueous solution Dosage be the 2% of organosiloxane monomer mixture gross mass, the dosage of emulsifier is that organosiloxane monomer mixes in aqueous solution Close the 7% of object gross mass；
B. the pH value of the mixed liquid B obtained by operation a is adjusted to 10, then adds in initiator, crosslinking agent and step（2）It is made Modified filler, it is 75 DEG C to keep whole temperature, be stirred continuously after processing 6h take out organic polysiloxane emulsion is spare；Institute The dosage for stating initiator is the 0.4% of mixed liquid B gross mass, and the dosage of the crosslinking agent is the 0.1% of mixed liquid B gross mass, institute The dosage for stating modified filler is the 7% of mixed liquid B gross mass；
（4）It is prepared by finished product synthetic leather：
By step（3）Organic polysiloxane emulsion obtained coats curing and synthesis is got product after in base fabric according to a conventional method Leather.
Further, step（1）Described in cyclic siloxane monomer for hexamethyl cyclotrisiloxane, described is multi-functional Group's siloxanyl monomers are methyltriethoxysilane, and the vinylsiloxane monomer is vinyltriethoxysilane.
Further, step（2）The volume fraction for operating ethyl alcohol in the ethanol solution described in a is 56%, the ammonium hydroxide Dripping quantity be the 18% of ethanol solution gross mass, the additive amount of the ethyl orthosilicate is the 5.2 of ethanol solution gross mass Times.
Further, step（2）The frequency for operating the supersound process described in a is 88kHz.
Further, step（2）Temperature when operating the drying process described in b in control drying box is 88 DEG C.
Further, step（3）Shearing rotating speed when operating the high speed shear processing described in a is 10000 revs/min.
Further, step（3）It is pyrovinic acid to operate the catalyst described in a, and the emulsifier is polyglycerol ester Fat acid esters.
Further, step（3）It is tert-butyl hydroperoxide to operate the initiator described in b, and the crosslinking agent is horse Take allyl propionate.
Further, step（4）Described in base fabric be looped fabric.
Embodiment 2
A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather, includes the following steps：
（1）Organosiloxane monomer mixture is prepared：
By cyclic siloxane monomer, function groups siloxanyl monomers and vinylsiloxane monomer correspondence according to weight ratio 68: 1.3:4, which carry out mixing, is put into agitator tank, and it is spare to obtain organosiloxane monomer mixture after high-speed stirred processing 33min；
（2）It is prepared by modified filler：
A. by cetyl dihydroxy ethyl amine oxide, nonylphenol polyoxyethylene ether and ethanol solution according to mass ratio 2:0.7：12 is common It is put into reaction kettle with mixing, after being stirred continuously processing 20min, then ammonium hydroxide is added dropwise into reaction kettle, is stirred continuously processing After 22min, then ethyl orthosilicate is added in into reaction kettle, it is spare to obtain mixture A after constantly supersound process 28min；
B. the modification mixed liquor of its gross mass 24% is added into the mixture A obtained by operation a, then heating is kept in reaction kettle Temperature for 74 DEG C, and the pressure in reaction kettle is increased into 0.46MPa, is filtered after being stirred continuously processing 30min, finally will The filter residue of gained be put into drying box be dried after 48min take out modified filler is spare；The modified mixed liquor is by such as The material composition of lower parts by weight：32 parts of chopped carbon fibers, 16 parts of nano-bentonite powder, 8 parts of titanate coupling agents, 7 parts of stearic acid Calcium, 6 parts of ethyl methacrylate, 5 parts of dimethyl carbonates, 5 parts of bacteria celluloses, 640 parts of water；
（3）Organic polysiloxane emulsion is prepared：
A. by step（1）The organosiloxane monomer mixture of gained is put into homogenizer, high speed shear processing 13min, so It puts into again in the aqueous solution dissolved with catalyst and emulsifier afterwards, it is 84 DEG C to keep whole temperature, is stirred continuously processing 7h It is spare that mixed liquid B is obtained afterwards；The gross mass of the organosiloxane monomer mixture is the 33% of water quality, catalyst in aqueous solution Dosage be the 3% of organosiloxane monomer mixture gross mass, the dosage of emulsifier is that organosiloxane monomer mixes in aqueous solution Close the 9% of object gross mass；
B. the pH value of the mixed liquid B obtained by operation a is adjusted to 10.5, then adds in initiator, crosslinking agent and step（2）System Modified filler, it is 78 DEG C to keep whole temperature, be stirred continuously after processing 7h take out organic polysiloxane emulsion is spare； The dosage of the initiator is the 0.5% of mixed liquid B gross mass, and the dosage of the crosslinking agent is the 0.2% of mixed liquid B gross mass, The dosage of the modified filler is the 8% of mixed liquid B gross mass；
（4）It is prepared by finished product synthetic leather：
By step（3）Organic polysiloxane emulsion obtained coats curing and synthesis is got product after in base fabric according to a conventional method Leather.
Further, step（1）Described in cyclic siloxane monomer for octamethylcy-clotetrasiloxane, described is multi-functional Group's siloxanyl monomers are vinyltrimethoxysilane, and the vinylsiloxane monomer is divinyl diethoxy silicon Alkane.
Further, step（2）The volume fraction for operating ethyl alcohol in the ethanol solution described in a is 57%, the ammonium hydroxide Dripping quantity be the 20% of ethanol solution gross mass, the additive amount of the ethyl orthosilicate is the 5.3 of ethanol solution gross mass Times.
Further, step（2）The frequency for operating the supersound process described in a is 91kHz.
Further, step（2）Temperature when operating the drying process described in b in control drying box is 90 DEG C.
Further, step（3）Shearing rotating speed when operating the high speed shear processing described in a is 11000 revs/min.
Further, step（3）It is ethylsulfonic acid to operate the catalyst described in a, and the emulsifier is propylene glycol fat Fat acid esters.
Further, step（3）It is lauroyl peroxide to operate the initiator described in b, and the crosslinking agent is diformazan Base acrylic acid binaryglycol ester.
Further, step（4）Described in base fabric be woven fabric.
Embodiment 3
A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather, includes the following steps：
（1）Organosiloxane monomer mixture is prepared：
By cyclic siloxane monomer, function groups siloxanyl monomers and vinylsiloxane monomer correspondence according to weight ratio 70: 1.5:5, which carry out mixing, is put into agitator tank, and it is spare to obtain organosiloxane monomer mixture after high-speed stirred processing 35min；
（2）It is prepared by modified filler：
A. by cetyl dihydroxy ethyl amine oxide, nonylphenol polyoxyethylene ether and ethanol solution according to mass ratio 2:0.7：13 is common It is put into reaction kettle with mixing, after being stirred continuously processing 22min, then ammonium hydroxide is added dropwise into reaction kettle, is stirred continuously processing After 24min, then ethyl orthosilicate is added in into reaction kettle, it is spare to obtain mixture A after constantly supersound process 30min；
B. the modification mixed liquor of its gross mass 26% is added into the mixture A obtained by operation a, then heating is kept in reaction kettle Temperature for 75 DEG C, and the pressure in reaction kettle is increased into 0.48MPa, is filtered after being stirred continuously processing 33min, finally will The filter residue of gained be put into drying box be dried after 50min take out modified filler is spare；The modified mixed liquor is by such as The material composition of lower parts by weight：34 parts of chopped carbon fibers, 18 parts of nano-bentonite powder, 9 parts of titanate coupling agents, 8 parts of stearic acid Calcium, 7 parts of ethyl methacrylate, 6 parts of dimethyl carbonates, 6 parts of bacteria celluloses, 660 parts of water；
（3）Organic polysiloxane emulsion is prepared：
A. by step（1）The organosiloxane monomer mixture of gained is put into homogenizer, high speed shear processing 15min, so It puts into again in the aqueous solution dissolved with catalyst and emulsifier afterwards, it is 86 DEG C to keep whole temperature, is stirred continuously processing 8h It is spare that mixed liquid B is obtained afterwards；The gross mass of the organosiloxane monomer mixture is the 35% of water quality, catalyst in aqueous solution Dosage be the 4% of organosiloxane monomer mixture gross mass, the dosage of emulsifier is that organosiloxane monomer mixes in aqueous solution Close the 10% of object gross mass；
B. the pH value of the mixed liquid B obtained by operation a is adjusted to 11, then adds in initiator, crosslinking agent and step（2）It is made Modified filler, it is 80 DEG C to keep whole temperature, be stirred continuously after processing 8h take out organic polysiloxane emulsion is spare；Institute The dosage for stating initiator is the 0.6% of mixed liquid B gross mass, and the dosage of the crosslinking agent is the 0.3% of mixed liquid B gross mass, institute The dosage for stating modified filler is the 9% of mixed liquid B gross mass；
（4）It is prepared by finished product synthetic leather：
By step（3）Organic polysiloxane emulsion obtained coats curing and synthesis is got product after in base fabric according to a conventional method Leather.
Further, step（1）Described in cyclic siloxane monomer for decamethylcyclopentaandoxane, described is multi-functional Group's siloxanyl monomers are phenyl triethoxysilane, and the vinylsiloxane monomer is vinyl methyl diethoxy silicon Alkane.
Further, step（2）The volume fraction for operating ethyl alcohol in the ethanol solution described in a is 58%, the ammonium hydroxide Dripping quantity be the 22% of ethanol solution gross mass, the additive amount of the ethyl orthosilicate is the 5.4 of ethanol solution gross mass Times.
Further, step（2）The frequency for operating the supersound process described in a is 94kHz.
Further, step（2）Temperature when operating the drying process described in b in control drying box is 92 DEG C.
Further, step（3）Shearing rotating speed when operating the high speed shear processing described in a is 12000 revs/min.
Further, step（3）It is acid dimethyl to operate the catalyst described in a, and the emulsifier is front three Base nonyl alcohol polyoxyethylene ether.
Further, step（3）It is cumyl peroxide to operate the initiator described in b, and the crosslinking agent is two Metering system acid propylene glycol ester.
Further, step（4）Described in base fabric be non-woven fabrics.
Comparative example 1
This comparative example 1 compared with Example 2, in step（3）Organic polysiloxane emulsion prepare in, with etc. mass parts city Sell silica substituting modification filler ingredient, method and step all same in addition to this.
Comparative example 2
This comparative example 2 compared with Example 2, in step（3）During organic polysiloxane emulsion is prepared, modified filler is eliminated Ingredient, method and step all same in addition to this.
Control group
Existing commercially available macromolecule silicon materials synthetic leather（Lotion used is prepared by the polymerization of single cyclic siloxane monomer）.
It is corresponding to above-described embodiment 2, comparative example 1, comparative example 2, control group in order to compare effect of the present invention Synthetic leather（Made resultant Leather specification all same, specifically lotion applicator thickness, base fabric material specification are identical）Carry out performance Test, specific correction data are as shown in table 1 below：
Table 1
Tensile strength（MPa） Elongation at break（%） High temperature resistant（℃） It is low temperature resistant（℃）
Embodiment 2 28.2 274.0 261 -55
Comparative example 1 24.0 242.1 244 -45
Comparative example 2 22.8 226.7 233 -40
Control group 21.3 214.5 224 -37
Note：Tensile strength and elongation at break described in upper table 1 are tested with reference to GB/T16491-2008；The resistance to height Temperature refers to the resistance to temperature of the indeformable highest of synthetic leather；The low temperature resistant minimum resistance to temperature for referring to synthetic leather and keeping softness.
The integrated quality of synthetic leather produced by the present invention has obtained apparent improvement, and its surface it can be seen from upper table 1 More smooth exquisiteness, feeling is better, and has good flame retardant property, and service life is up to 20 years, great application value.

Claims (9)

1. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather, which is characterized in that include the following steps：
（1）Organosiloxane monomer mixture is prepared：
By cyclic siloxane monomer, function groups siloxanyl monomers and vinylsiloxane monomer correspondence according to weight ratio 65 ~ 70: 0.8~1.5:3 ~ 5, which carry out mixing, is put into agitator tank, and high-speed stirred obtains the mixing of organosiloxane monomer after handling 30 ~ 35min Object is spare；
（2）It is prepared by modified filler：
A. by cetyl dihydroxy ethyl amine oxide, nonylphenol polyoxyethylene ether and ethanol solution according to mass ratio 2:0.7：10~ 13 common mixing are put into reaction kettle, after being stirred continuously 18 ~ 22min of processing, then ammonium hydroxide are added dropwise into reaction kettle, are stirred continuously After handling 20 ~ 24min, then ethyl orthosilicate is added in into reaction kettle, it is standby to obtain mixture A after constantly 25 ~ 30min of supersound process With；
B. the modification mixed liquor of its gross mass 22 ~ 26% is added into the mixture A obtained by operation a, then heating keeps reaction kettle Interior temperature is 72 ~ 75 DEG C, and the pressure in reaction kettle is increased to 0.44 ~ 0.48MPa, and it is laggard to be stirred continuously 28 ~ 33min of processing Row filtering, finally by the filter residue of gained be put into drying box be dried 45 ~ 50min after take out modified filler is spare；Institute State material composition of the modified mixed liquor by following parts by weight：30 ~ 34 parts of chopped carbon fibers, 14 ~ 18 parts of nano-bentonite powder, 5 ~ 9 Part titanate coupling agent, 6 ~ 8 parts of calcium stearates, 4 ~ 7 parts of ethyl methacrylate, 4 ~ 6 parts of dimethyl carbonates, 3 ~ 6 parts of bacterium fibres Dimension element, 620 ~ 660 parts of water；
（3）Organic polysiloxane emulsion is prepared：
A. by step（1）The organosiloxane monomer mixture of gained is put into homogenizer, and high speed shear handles 10 ~ 15min, Then it puts into again in the aqueous solution dissolved with catalyst and emulsifier, it is 82 ~ 86 DEG C to keep whole temperature, is stirred continuously place It is spare that mixed liquid B is obtained after 5 ~ 8h of reason；The gross mass of the organosiloxane monomer mixture is the 30 ~ 35% of water quality, aqueous solution The dosage of middle catalyst is the 2 ~ 4% of organosiloxane monomer mixture gross mass, and the dosage of emulsifier is organosilicon in aqueous solution The 7 ~ 10% of oxygen alkane monomer mixture gross mass；
B. the pH value of the mixed liquid B obtained by operation a is adjusted to 10 ~ 11, then adds in initiator, crosslinking agent and step（2）System The modified filler obtained, it is 75 ~ 80 DEG C to keep whole temperature, and organic polysiloxane emulsion is taken out to obtain after being stirred continuously 6 ~ 8h of processing It is spare；The dosage of the initiator is the 0.4 ~ 0.6% of mixed liquid B gross mass, and the dosage of the crosslinking agent is the total matter of mixed liquid B The 0.1 ~ 0.3% of amount, the dosage of the modified filler is the 7 ~ 9% of mixed liquid B gross mass；
（4）It is prepared by finished product synthetic leather：
By step（3）Organic polysiloxane emulsion obtained coats curing and synthesis is got product after in base fabric according to a conventional method Leather.
2. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（1）Described in cyclic siloxane monomer for hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethyl ring Any one in five siloxanes, the function groups siloxanyl monomers are methyltriethoxysilane, vinyl trimethoxy Any one in base silane, phenyl triethoxysilane, the vinylsiloxane monomer are vinyl triethoxyl silicon Any one in alkane, divinyl diethoxy silane, vinyl methyl diethoxy silane.
3. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（2）The volume fraction for operating ethyl alcohol in the ethanol solution described in a is 56 ~ 58%, and the dripping quantity of the ammonium hydroxide is The 18 ~ 22% of ethanol solution gross mass, the additive amount of the ethyl orthosilicate are 5.2 ~ 5.4 times of ethanol solution gross mass.
4. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（2）The frequency for operating the supersound process described in a is 88 ~ 94kHz.
5. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（2）Temperature when operating the drying process described in b in control drying box is 88 ~ 92 DEG C.
6. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（3）Shearing rotating speed when operating the high speed shear processing described in a is 10000 ~ 12000 revs/min.
7. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（3）The catalyst operated described in a is pyrovinic acid, ethylsulfonic acid, any one in acid dimethyl, institute The emulsifier stated is any one in polyglyceryl fatty acid ester, methyl glycol fatty acid ester, Exxal 12 polyoxyethylene ether.
8. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（3）The initiator operated described in b is tert-butyl hydroperoxide, in lauroyl peroxide, cumyl peroxide Any one, the crosslinking agent is Malaysia allyl propionate, diethyleneglycol dimethacrylate, dimethyl allene acid propylene glycol Any one in ester.
9. a kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather according to claim 1, feature exist In step（4）Described in base fabric be looped fabric, woven fabric, any one in non-woven fabrics.
CN201711454409.0A 2017-12-28 2017-12-28 A kind of preparation method of heat-resistant, high strength degree macromolecule silicon materials synthetic leather Pending CN108203885A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112251098A (en) * 2020-11-03 2021-01-22 王洪磊 Waterproof heat-insulation exterior wall coating for building and preparation method thereof
WO2023221226A1 (en) * 2022-05-18 2023-11-23 浙江嘉柯新材料科技有限公司 Environmentally-friendly water-based synthetic leather and production process therefor

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CN105603768A (en) * 2016-03-15 2016-05-25 惠州赛力珑新材料有限公司 Burn-resistant synthetic leather and production method
CN105820615A (en) * 2016-04-15 2016-08-03 安徽开林新材料股份有限公司 Environment friendly aluminum electrode anticorrosive paint and preparation method thereof
CN106149392A (en) * 2016-08-17 2016-11-23 颍上县亿达帐蓬有限公司 A kind of low temperature resistant cold-resistant canvas tent fabric and preparation method thereof
CN106866971A (en) * 2017-04-10 2017-06-20 广东优科艾迪高分子材料有限公司 A kind of weather-proof low-temperature type organosilicon impact modifier and preparation method and application

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Publication number Priority date Publication date Assignee Title
CN105603768A (en) * 2016-03-15 2016-05-25 惠州赛力珑新材料有限公司 Burn-resistant synthetic leather and production method
CN105820615A (en) * 2016-04-15 2016-08-03 安徽开林新材料股份有限公司 Environment friendly aluminum electrode anticorrosive paint and preparation method thereof
CN106149392A (en) * 2016-08-17 2016-11-23 颍上县亿达帐蓬有限公司 A kind of low temperature resistant cold-resistant canvas tent fabric and preparation method thereof
CN106866971A (en) * 2017-04-10 2017-06-20 广东优科艾迪高分子材料有限公司 A kind of weather-proof low-temperature type organosilicon impact modifier and preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112251098A (en) * 2020-11-03 2021-01-22 王洪磊 Waterproof heat-insulation exterior wall coating for building and preparation method thereof
WO2023221226A1 (en) * 2022-05-18 2023-11-23 浙江嘉柯新材料科技有限公司 Environmentally-friendly water-based synthetic leather and production process therefor

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Application publication date: 20180626