CN110079262A - A kind of preparation method of automotive interior material composite adhesive - Google Patents
A kind of preparation method of automotive interior material composite adhesive Download PDFInfo
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- CN110079262A CN110079262A CN201910181994.4A CN201910181994A CN110079262A CN 110079262 A CN110079262 A CN 110079262A CN 201910181994 A CN201910181994 A CN 201910181994A CN 110079262 A CN110079262 A CN 110079262A
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- 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
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- 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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Medicinal Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of preparation methods of automotive interior material composite adhesive, belong to adhesive technology field.The present invention is pressed rice hull cellulose, biogas slurry, sucrose, water mixed fermentation, filtering, freezing, ball milling is dry, and charing obtains modified fibre, polyether polyol is placed in reaction kettle, is heated up, vacuum dehydration is cooling, it is subsequently added into isocyanates and promotor, constant temperature is stirred to react, and is subsequently added into chloroform, chlorobenzoyl chloride, phosphatide, organic acid, plants essential oil, grease, mica powder is stirred, and is discharged to get automotive interior material composite adhesive.Automotive interior material provided by the invention has excellent adhesive property with composite adhesive.
Description
Technical field
The invention discloses a kind of preparation methods of automotive interior material composite adhesive, belong to adhesive technology neck
Domain.
Background technique
Adhesive for polyurethane is the adhesive in strand containing urethano or isocyanates base class.It develops first within 1940
Adhesive for polyurethane is bonding with buna for metal out, and dual-component polyurethane adhesive starts to obtain wide after the fifties
General application has gradually formed glutinous including polyisocyanates solvent adhesive, bi-component polyurethane rouge adhesive, one-component polyurethane
The multiple types such as agent, Aqueous Polyurethane Adhesives, hot melt type polyurethane adhesive, polyurethane sealant, and opened after the sixties
Beginning is applied in auto industry.
There are many adhesive type used in auto industry, are divided into vehicle body glue, inside gadget glue, brake block by purposes and use
Glue, windshield glass sealant and faying face liquid sealant etc., adhesive and sealant solve the problems, such as " three leakages " of automobile, no
Only play the role of enhancing vehicle structure, heat-insulated vibration damping and internal and external ornament, and simplify automobile manufacturing process, in automobile light weight
Change, is energy-saving, the aspect that prolongs the service life plays an increasingly important role.
New automobile structure makes automotive upholstery adhesive glue grow at top speed, and wherein roof of the vehicle adhesive is for will be soft
Ceiling materials paste on car body top cover, increase interior beauty, roof of the vehicle have polyvinyl chloride film composite polyurethane foam or
Soft ceiling of fabric composite polyurethane foam etc..Contain highly polar and chemically active group in adhesive for polyurethane, to foam plastic
The material of any surface finish such as the porous materials such as material, timber, leather, fabric, paper, ceramics and metal, glass, rubber, plastics is all
There is excellent adhesive property；And by adjusting soft segment in adhesive for polyurethane and hard section ratio and structure, solidfied material can have not
With hardness and elongation, glue-line is adjustable from flexibility to rigidity, while soft-hard transition zone is formed between metal/non-metal material,
It is very suitable to the bonding of ceiling, is all widely applied in automobile industry, is quickly grown.
For the needs for adapting to automatic production line in auto industry, the curing rate of adhesive must quickly, and polyurethane
Adhesive, which generallys use, is added the methods of organic tin, amine type accelerator to improve curing rate, this makes its performance have occurred one
The storage period of fixed variation, especially adhesive and validity period are greatly affected.Certain accessory factory, is used using adhesive for polyurethane
It in the bonding of ceiling, needs improving curing rate using preceding addition promotor to guarantee the continuous productive process on production line, and matches
The adhesive made only has the working life of 4h or so, and working life summer is shorter, influences its production efficiency.There is researcher to invent one
Kind adhesive for automobile interiors, by following components, part is formed according to the weight ratio: 8~15 parts of epoxy resin, 6~10 parts of clay,
3~5 parts of water-based isocyanate, 5~8 parts of aqueous modified rosin resin, 4~6 parts of coupling agent, 2~4 parts of vulcanizing agent, tackifier 1~
3 parts, 5~10 parts of organic solvent.The adhesive for automobile interiors that the invention obtains, its technical effect is that using the original of low toxic and environment-friendly
Material, material manufacture adhesive for automobile interiors, to make it compared with existing product, not only cohesive force with super strength,
But also with no benzene, without environmental advantages such as aldehyde.But there is also caking property for the glutinous agent of Polyurethane adhesive traditional at present
The problem of capable of can not further increasing, therefore also need to study it.
Summary of the invention
The present invention solves the technical problem of: it can not be into for orthodox car interior material adhesive adhesive property
The problem of one step improves, provides a kind of preparation method of automotive interior material composite adhesive.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
(1) according to parts by weight, by 20~30 parts of rice hull celluloses, 2~3 parts of biogas slurries, 1~2 portion of sucrose, 30~50 parts of water mixing hairs
Ferment filters, freezing, and ball milling is dry, and charing obtains modified fibre；
(2) according to parts by weight, 20~30 parts of isocyanates, 40~60 parts of polyether polyol, 10~20 part of three chloromethane are successively taken
Alkane, 3~5 parts of promotors, 5~8 parts of chlorobenzoyl chlorides, 10~20 parts of modified fibres, 8~10 parts of modified auxiliary materials, 3~5 parts of phosphatide, 3
~5 parts of organic acids, 2~3 parts of plants essential oils, 2~3 parts of greases, 2~3 parts of mica powders；
(3) polyether polyol being placed in reaction kettle, is heated up, vacuum dehydration is cooling, it is subsequently added into isocyanates and promotor,
Constant temperature is stirred to react, and is subsequently added into chloroform, chlorobenzoyl chloride, phosphatide, organic acid, plants essential oil, grease, mica powder, stirring
Mixing discharges to get automotive interior material composite adhesive.
Step (2) isocyanates is methyl diphenylene diisocyanate, toluene di-isocyanate(TDI) or isophorone two
Any one in isocyanates.
Step (2) polyether polyol is polyoxypropyleneglycol, polyoxytetramethylene glycol or tetrahydrofuran-oxidation
Any one in propylene copolymer glycols.
Step (2) promotor is stannous octoate, any one in isooctyl acid lead or dibutyl tin dilaurate.
The preparation process of step (2) the modified auxiliary material are as follows: according to parts by weight, by 8~10 parts of white carbon blacks, 5~8 parts of charcoals
Black, 3~5 parts of silver nitrates, 3~5 parts of ammonium chlorides, 30~40 parts of water mixing and ball millings obtain No. 1 mixed liquor, according to parts by weight, by 20
~30 parts of acrylonitrile, 5~8 parts of azodiisobutyronitriles, 5~8 parts of pentanes, 5~8 parts of methyl methacrylate mixing ultrasounds obtain 2
Number mixed liquor；No. 2 mixed liquors and No. 1 mixed liquor 1:5~1:10 low-temperature and high-speed in mass ratio are sheared, nitrogen charging high pressure heat-preserving is anti-
It answers, cools down, pressure release discharges, and filters, and washing obtains modified auxiliary material.
Step (2) phosphatide is soybean lecithin, any one in milk phosphatide or yolk phospholipid.
Step (2) organic acid is linoleic acid, any one in humic acid or rich dimension acid.
Step (2) plants essential oil is Rosemary Oil, Lavender, rose ethereal oil, jasmine essential oil, camellia
Any one in essential oil or saussurea involucrata essential oil.
Step (2) grease is glycerin monostearate, single glyceryl linolenate, bi-tristearin or double flax
Any one in acid glyceride.
Step (2) mica powder is any one in white mica powder, black clouds female powder or phlogopite powder.
The beneficial effects of the present invention are:
(1) present invention is by adding modified auxiliary material, and during the preparation process, silver nitrate is reacted with ammonium chloride, generates silver nitride precipitation
And ammonium nitrate, the silver nitride precipitation of generation are attached to cladding film surface, increase the roughness on modified auxiliary material surface, so that modified
Effective contact area between matrix resin on auxiliary material surface, so that the adhesion strength of system gets a promotion, in mixing process,
The heated volatilization of the organic solvent coated in modified auxiliary material, so that modified auxiliary material volume increases, in heating sulfidation, You Jirong
Agent volatilization, so that modified auxiliary material volume continues to expand, on the one hand, increase the elasticity of system, on the other hand, be modified the swollen of auxiliary material
Swollen stress is compacted system further, and on the other hand, the swelling stress of modified filler obtains system further
Compacting, the consistency of system is increased, to further improve the adhesive property of system；
(2) present invention is by addition modified fibre, firstly, by rice hull cellulose, biogas slurry, sucrose, water mixed fermentation utilizes microorganism
The enzyme of generation decomposes the organic matter in rice hull cellulose, so that interfibrous interface bond strength further declines, so that between fiber
Gap further widened, enable moisture is good to penetrate into system, be then passed through liquid nitrogen frozen, so that fiber
Between form ice crystal, be then passed through ball milling, the rupture of ice crystal is so that fibrocyte ruptures, so that fiber splits into micro/nano level
Whisker, be then passed through charing so that the rice hull cellulose of micro/nano level carbonizes, due to rice hull cellulose surface contain it is siliceous, it is internal
Organic matter shunk in carbonization process, and the contraction of extraneous siliceous obstruction fiber, from the fiber for making micro/nano level
Whisker occurs helix-coil and is stung in use since machinery can occur between the fibrous crystal palpus of spiral helicine micro/nano level
It closes, so that the adhesive property of system gets a promotion, in addition, can generate a large amount of tar in carbonization process, tar can
The interface bond strength between modified fibre and matrix is penetrated into, so that the adhesion strength of system is further promoted.
Specific embodiment
According to parts by weight, by 8~10 parts of white carbon blacks, 5~8 parts of carbon blacks, 3~5 parts of silver nitrates, 3~5 parts of ammonium chlorides, 30
~40 parts of water are placed in 30~50min of ball milling mixing in ball mill, obtain No. 1 mixed liquor；According to parts by weight, by 20~30 parts of propylene
Nitrile, 5~8 parts of azodiisobutyronitriles, 5~8 parts of pentanes, 5~8 parts of methyl methacrylates are placed in No. 1 beaker, and by No. 1
Beaker is placed in ultrasonic disperse instrument, under the conditions of supersonic frequency is 55~75kHz, is mixed 30~50min of ultrasound, is obtained No. 2 mixing
Liquid；By No. 2 mixed liquors and No. 1 mixed liquor 1:5~1:8 in mass ratio be placed in shearing homogenizer in, in temperature be 1~10 DEG C of condition
Under, low-temperature and high-speed shears 5~10min, obtains homogeneous mixed liquor, then homogeneous mixed liquor is placed in autoclave, and with 60
~90mL/min rate is filled with nitrogen into reaction kettle, and in 0.6~0.9MPa of pressure, temperature is 60~70 DEG C, and nitrogen charging heat preservation is protected
After 30~50min of pressure reaction, reaction under high pressure temperature in the kettle is cooled to room temperature, opens valve pressure release, discharging obtains mixed serum,
Mixed serum is filtered again, obtains filter cake, Washing of Filter Cake 5~8 is then obtained into modified auxiliary material with deionized water；According to parts by weight,
By 20~30 parts of rice hull celluloses, 2~3 parts of biogas slurries, 1~2 portion of sucrose, 30~50 parts of water are placed in fermentation cauldron, in temperature be 30~
It 35 DEG C, under the conditions of revolving speed is 100~200r/min, is stirred fermentation 3~5 days, obtains fermentation mixed liquor, then the mixed liquor that will ferment
Filtering, obtains filter residue, then filter residue is placed in liquid nitrogen and is freezed, must freeze material, and freezing material is then placed in ball milling in ball mill, is obtained
Ball milling material is then placed in baking oven by ball milling material, and under the conditions of temperature is 105~110, drying to constant weight obtains dry ball abrasive material,
Then ball milling material is placed in retort, and nitrogen is filled with into furnace with the rate of 60~90mL/min, in temperature be 750~
Under the conditions of 850 DEG C, after carbonizing 2~3h, it is down to room temperature with furnace, obtains modified fibre；According to parts by weight, successively take 20~30 parts it is different
Cyanate, 40~60 parts of polyether polyol, 10~20 parts of chloroforms, 3~5 parts of promotors, 5~8 parts of chlorobenzoyl chlorides, 10~20
Part modified fibre, 8~10 parts of modified auxiliary materials, 3~5 parts of phosphatide, 3~5 parts of organic acids, 2~3 parts of plants essential oils, 2~3 parts of greases,
2~3 parts of mica powders；Polyether polyol is placed in reaction kettle, is warming up to 120~130 DEG C, under the conditions of pressure is 2~3kPa,
After vacuum dehydration 4h, be cooled to 60 DEG C, be subsequently added into isocyanates and promotor, in temperature be 60 DEG C, revolving speed be 300~
Under the conditions of 500r/min, constant temperature is stirred to react 2~3h, and chloroform, chlorobenzoyl chloride are then added into reaction kettle, and phosphatide has
Machine acid, plants essential oil, grease, mica powder, under the conditions of revolving speed is 400~600r/min, after being stirred 40~60min, out
Material is to get automotive interior material composite adhesive.The isocyanates is methyl diphenylene diisocyanate, toluene diisocyanate
Any one in acid esters or isophorone diisocyanate.The polyether polyol is polyoxypropyleneglycol, and polyoxy four is sub-
Any one in methyl glycol or tetrahydrofuran-propylene oxide copolymer glycols.The promotor is stannous octoate, isooctyl acid lead
Or any one in dibutyl tin dilaurate.The phosphatide is soybean lecithin, any in milk phosphatide or yolk phospholipid
It is a kind of.The organic acid is linoleic acid, any one in humic acid or rich dimension acid.The plants essential oil is Rosemary Oil,
Any one in Lavender, rose ethereal oil, jasmine essential oil, camellia essential oil or saussurea involucrata essential oil.The grease is single
Any one in tristerin, single glyceryl linolenate, bi-tristearin or double glyceryl linolenates.The cloud
Female powder is any one in white mica powder, black clouds female powder or phlogopite powder.
According to parts by weight, by 10 parts of white carbon blacks, 8 parts of carbon blacks, 5 parts of silver nitrates, 5 parts of ammonium chlorides, 40 parts of water are placed in ball milling
Ball milling mixing 50min in machine obtains No. 1 mixed liquor；According to parts by weight, by 30 parts of acrylonitrile, 8 parts of azodiisobutyronitriles, 8 parts just
Pentane, 8 parts of methyl methacrylates are placed in No. 1 beaker, and No. 1 beaker is placed in ultrasonic disperse instrument, are in supersonic frequency
Under the conditions of 75kHz, ultrasound 50min is mixed, No. 2 mixed liquors are obtained；No. 2 mixed liquors are placed in No. 1 mixed liquor 1:8 in mass ratio and are cut
It cuts in homogenizer, under the conditions of temperature is 10 DEG C, low-temperature and high-speed shears 10min, homogeneous mixed liquor is obtained, then by homogeneous mixed liquor
It is placed in autoclave, and nitrogen is filled with into reaction kettle with 90mL/min rate, in pressure 0.9MPa, temperature is 70 DEG C,
After nitrogen charging heat-insulation pressure keeping reacts 50min, reaction under high pressure temperature in the kettle is cooled to room temperature, opens valve pressure release, discharging must mix
Slurries, then mixed serum is filtered, filter cake is obtained, Washing of Filter Cake 8 is then obtained into modified auxiliary material with deionized water；In parts by weight
Meter, by 30 parts of rice hull celluloses, 3 parts of biogas slurries, 2 portions of sucrose, 50 parts of water are placed in fermentation cauldron, in temperature be 35 DEG C, revolving speed 200r/
Under the conditions of min, it is stirred fermentation 5 days, fermentation mixed liquor is obtained, then fermentation mixed liquor is filtered, obtains filter residue, then set filter residue
It is freezed in liquid nitrogen, material must be freezed, freezing material is then placed in ball milling in ball mill, ball milling material is obtained, is then placed in ball milling material
In baking oven, under the conditions of temperature is 110, drying to constant weight obtains dry ball abrasive material, then ball milling material is placed in retort, and
It is filled with nitrogen into furnace with the rate of 90mL/min, under the conditions of temperature is 850 DEG C, after carbonizing 3h, is down to room temperature with furnace, must change
Property fiber；According to parts by weight, 30 parts of isocyanates are successively taken, 60 parts of polyether polyol, 20 parts of chloroforms, 5 parts of promotors,
8 parts of chlorobenzoyl chlorides, 20 parts of modified fibres, 10 parts of modified auxiliary materials, 5 parts of phosphatide, 5 parts of organic acids, 3 parts of plants essential oils, 3 parts of greases, 3
Part mica powder；Polyether polyol is placed in reaction kettle, is warming up to 130 DEG C, under the conditions of pressure is 3kPa, vacuum dehydration 4h
Afterwards, 60 DEG C are cooled to, isocyanates and promotor are subsequently added into, in temperature be 60 DEG C, revolving speed be 500r/min under the conditions of, constant temperature
It is stirred to react 3h, chloroform, chlorobenzoyl chloride, phosphatide, organic acid, plants essential oil, grease, mica are then added into reaction kettle
Powder after being stirred 60min, discharges under the conditions of revolving speed is 600r/min to get automotive interior material composite adhesive.
The isocyanates is methyl diphenylene diisocyanate.The polyether polyol is polyoxypropyleneglycol.The promotor
For stannous octoate.The phosphatide is soybean lecithin.The organic acid is linoleic acid.The plants essential oil is Rosemary Oil.Institute
Stating grease is glycerin monostearate.The mica powder is white mica powder.
According to parts by weight, by 10 parts of white carbon blacks, 8 parts of carbon blacks, 5 parts of silver nitrates, 5 parts of ammonium chlorides, 40 parts of water are placed in ball milling
Ball milling mixing 50min in machine obtains No. 1 mixed liquor；According to parts by weight, by 30 parts of acrylonitrile, 8 parts of azodiisobutyronitriles, 8 parts just
Pentane, 8 parts of methyl methacrylates are placed in No. 1 beaker, and No. 1 beaker is placed in ultrasonic disperse instrument, are in supersonic frequency
Under the conditions of 75kHz, ultrasound 50min is mixed, No. 2 mixed liquors are obtained；No. 2 mixed liquors are placed in No. 1 mixed liquor 1:8 in mass ratio and are cut
It cuts in homogenizer, under the conditions of temperature is 10 DEG C, low-temperature and high-speed shears 10min, homogeneous mixed liquor is obtained, then by homogeneous mixed liquor
It is placed in autoclave, and nitrogen is filled with into reaction kettle with 90mL/min rate, in pressure 0.9MPa, temperature is 70 DEG C,
After nitrogen charging heat-insulation pressure keeping reacts 50min, reaction under high pressure temperature in the kettle is cooled to room temperature, opens valve pressure release, discharging must mix
Slurries, then mixed serum is filtered, filter cake is obtained, Washing of Filter Cake 8 is then obtained into modified auxiliary material with deionized water；In parts by weight
Meter, successively takes 30 parts of isocyanates, 60 parts of polyether polyol, 20 parts of chloroforms, 5 parts of promotors, 8 parts of chlorobenzoyl chlorides, and 10 parts
Modified auxiliary material, 5 parts of phosphatide, 5 parts of organic acids, 3 parts of plants essential oils, 3 parts of greases, 3 parts of mica powders；Polyether polyol is placed in reaction
In kettle, 130 DEG C are warming up to, under the conditions of pressure is 3kPa, after vacuum dehydration 4h, 60 DEG C is cooled to, is subsequently added into isocyanates
And promotor, it is 60 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred to react 3h, is then added into reaction kettle
Chloroform, chlorobenzoyl chloride, phosphatide, organic acid, plants essential oil, grease, mica powder stir under the conditions of revolving speed is 600r/min
After mixing mixing 60min, discharge to get automotive interior material composite adhesive.The isocyanates is that diphenyl methane two is different
Cyanate.The polyether polyol is polyoxypropyleneglycol.The promotor is stannous octoate.The phosphatide is soybean phosphorus
Rouge.The organic acid is linoleic acid.The plants essential oil is Rosemary Oil.The grease is glycerin monostearate.It is described
Mica powder is white mica powder.
According to parts by weight, by 30 parts of rice hull celluloses, 3 parts of biogas slurries, 2 portions of sucrose, 50 parts of water are placed in fermentation cauldron, Yu Wendu
It is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, obtains fermentation mixed liquor, then fermentation mixed liquor is filtered,
Filter residue is obtained, then filter residue is placed in liquid nitrogen and is freezed, material must be freezed, freezing material is then placed in ball milling in ball mill, obtains ball milling
Ball milling material, is then placed in baking oven by material, dry to constant weight under the conditions of temperature is 110, dry ball abrasive material is obtained, then by ball
Abrasive material is placed in retort, and nitrogen is filled with into furnace with the rate of 90mL/min, under the conditions of temperature is 850 DEG C, carbonizes 3h
Afterwards, it is down to room temperature with furnace, obtains modified fibre；According to parts by weight, 30 parts of isocyanates are successively taken, 60 parts of polyether polyol, 20
Part chloroform, 5 parts of promotors, 8 parts of chlorobenzoyl chlorides, 20 parts of modified fibres, 5 parts of phosphatide, 5 parts of organic acids, 3 parts of plants essential oils, 3
Part grease, 3 parts of mica powders；Polyether polyol is placed in reaction kettle, is warming up to 130 DEG C, under the conditions of pressure is 3kPa, vacuum
After being dehydrated 4h, 60 DEG C are cooled to, isocyanates and promotor are subsequently added into, is 60 DEG C in temperature, revolving speed is 500r/min condition
Under, constant temperature is stirred to react 3h, and chloroform, chlorobenzoyl chloride, phosphatide, organic acid, plants essential oil, oil are then added into reaction kettle
Rouge, mica powder, under the conditions of revolving speed is 600r/min, after being stirred 60min, discharging is to get automotive interior material with compound
Adhesive.The isocyanates is methyl diphenylene diisocyanate.The polyether polyol is polyoxypropyleneglycol.It is described
Promotor is stannous octoate.The phosphatide is soybean lecithin.The organic acid is linoleic acid.The plants essential oil is rosemary essence
Oil.The grease is glycerin monostearate.The mica powder is white mica powder.
According to parts by weight, by 10 parts of white carbon blacks, 8 parts of carbon blacks, 5 parts of silver nitrates, 5 parts of ammonium chlorides, 40 parts of water are placed in ball milling
Ball milling mixing 50min in machine obtains No. 1 mixed liquor；According to parts by weight, by 30 parts of acrylonitrile, 8 parts of azodiisobutyronitriles, 8 parts just
Pentane, 8 parts of methyl methacrylates are placed in No. 1 beaker, and No. 1 beaker is placed in ultrasonic disperse instrument, are in supersonic frequency
Under the conditions of 75kHz, ultrasound 50min is mixed, No. 2 mixed liquors are obtained；No. 2 mixed liquors are placed in No. 1 mixed liquor 1:8 in mass ratio and are cut
It cuts in homogenizer, under the conditions of temperature is 10 DEG C, low-temperature and high-speed shears 10min, homogeneous mixed liquor is obtained, then by homogeneous mixed liquor
It is placed in autoclave, and nitrogen is filled with into reaction kettle with 90mL/min rate, in pressure 0.9MPa, temperature is 70 DEG C,
After nitrogen charging heat-insulation pressure keeping reacts 50min, reaction under high pressure temperature in the kettle is cooled to room temperature, opens valve pressure release, discharging must mix
Slurries, then mixed serum is filtered, filter cake is obtained, Washing of Filter Cake 8 is then obtained into modified auxiliary material with deionized water；In parts by weight
Meter, by 30 parts of rice hull celluloses, 3 parts of biogas slurries, 2 portions of sucrose, 50 parts of water are placed in fermentation cauldron, in temperature be 35 DEG C, revolving speed 200r/
Under the conditions of min, it is stirred fermentation 5 days, fermentation mixed liquor is obtained, then fermentation mixed liquor is filtered, obtains filter residue, then set filter residue
It is freezed in liquid nitrogen, material must be freezed, freezing material is then placed in ball milling in ball mill, ball milling material is obtained, is then placed in ball milling material
In baking oven, under the conditions of temperature is 110, drying to constant weight obtains dry ball abrasive material, then ball milling material is placed in retort, and
It is filled with nitrogen into furnace with the rate of 90mL/min, under the conditions of temperature is 850 DEG C, after carbonizing 3h, is down to room temperature with furnace, must change
Property fiber；According to parts by weight, 30 parts of isocyanates are successively taken, 60 parts of polyether polyol, 20 parts of chloroforms, 5 parts of promotors,
8 parts of chlorobenzoyl chlorides, 20 parts of modified fibres, 10 parts of modified auxiliary materials, 5 parts of organic acids, 3 parts of plants essential oils, 3 parts of greases, 3 parts of micas
Powder；Polyether polyol is placed in reaction kettle, is warming up to 130 DEG C, it is cooling after vacuum dehydration 4h under the conditions of pressure is 3kPa
To 60 DEG C, it is subsequently added into isocyanates and promotor, is 60 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature stirring is anti-
3h is answered, is then added chloroform into reaction kettle, chlorobenzoyl chloride, organic acid, plants essential oil, grease, mica powder is in revolving speed
Under the conditions of 600r/min, after being stirred 60min, discharge to get automotive interior material composite adhesive.The isocyanates
For methyl diphenylene diisocyanate.The polyether polyol is polyoxypropyleneglycol.The promotor is stannous octoate.Institute
Stating organic acid is linoleic acid.The plants essential oil is Rosemary Oil.The grease is glycerin monostearate.The mica powder
For white mica powder.
According to parts by weight, by 10 parts of white carbon blacks, 8 parts of carbon blacks, 5 parts of silver nitrates, 5 parts of ammonium chlorides, 40 parts of water are placed in ball milling
Ball milling mixing 50min in machine obtains No. 1 mixed liquor；According to parts by weight, by 30 parts of acrylonitrile, 8 parts of azodiisobutyronitriles, 8 parts just
Pentane, 8 parts of methyl methacrylates are placed in No. 1 beaker, and No. 1 beaker is placed in ultrasonic disperse instrument, are in supersonic frequency
Under the conditions of 75kHz, ultrasound 50min is mixed, No. 2 mixed liquors are obtained；No. 2 mixed liquors are placed in No. 1 mixed liquor 1:8 in mass ratio and are cut
It cuts in homogenizer, under the conditions of temperature is 10 DEG C, low-temperature and high-speed shears 10min, homogeneous mixed liquor is obtained, then by homogeneous mixed liquor
It is placed in autoclave, and nitrogen is filled with into reaction kettle with 90mL/min rate, in pressure 0.9MPa, temperature is 70 DEG C,
After nitrogen charging heat-insulation pressure keeping reacts 50min, reaction under high pressure temperature in the kettle is cooled to room temperature, opens valve pressure release, discharging must mix
Slurries, then mixed serum is filtered, filter cake is obtained, Washing of Filter Cake 8 is then obtained into modified auxiliary material with deionized water；In parts by weight
Meter, by 30 parts of rice hull celluloses, 3 parts of biogas slurries, 2 portions of sucrose, 50 parts of water are placed in fermentation cauldron, in temperature be 35 DEG C, revolving speed 200r/
Under the conditions of min, it is stirred fermentation 5 days, fermentation mixed liquor is obtained, then fermentation mixed liquor is filtered, obtains filter residue, then set filter residue
It is freezed in liquid nitrogen, material must be freezed, freezing material is then placed in ball milling in ball mill, ball milling material is obtained, is then placed in ball milling material
In baking oven, under the conditions of temperature is 110, drying to constant weight obtains dry ball abrasive material, then ball milling material is placed in retort, and
It is filled with nitrogen into furnace with the rate of 90mL/min, under the conditions of temperature is 850 DEG C, after carbonizing 3h, is down to room temperature with furnace, must change
Property fiber；According to parts by weight, 30 parts of isocyanates are successively taken, 60 parts of polyether polyol, 20 parts of chloroforms, 5 parts of promotors,
8 parts of chlorobenzoyl chlorides, 20 parts of modified fibres, 10 parts of modified auxiliary materials, 5 parts of phosphatide, 3 parts of plants essential oils, 3 parts of greases, 3 parts of mica powders,
Polyether polyol is placed in reaction kettle, is warming up to 130 DEG C, under the conditions of pressure is 3kPa, after vacuum dehydration 4h, is cooled to 60
DEG C, it is subsequently added into isocyanates and promotor, is 60 DEG C in temperature, under the conditions of revolving speed is 500r/min, constant temperature is stirred to react 3h,
Then be added chloroform into reaction kettle, chlorobenzoyl chloride, phosphatide, plants essential oil, grease, mica powder, in revolving speed be 600r/
Under the conditions of min, after being stirred 60min, discharge to get automotive interior material composite adhesive.The isocyanates is two
Methylenebis phenyl isocyanate.The polyether polyol is polyoxypropyleneglycol.The promotor is stannous octoate.The phosphorus
Rouge is soybean lecithin.The plants essential oil is Rosemary Oil.The grease is glycerin monostearate.The mica powder is white
Mica powder.
1 to 5 gained automotive interior material of example is subjected to performance detection with composite adhesive, the specific detection method is as follows:
By on above-mentioned adhesive spraying to car body sticky surface, through 80 DEG C of drying tunnel dry out solvent, it is placed on specified pressing machine, and it is interior
Exterior material is compound through 130 DEG C of 5s hot pressing, after being cooled to room temperature, tests the adhesive strength of interior material and car body.
Specific testing result is as shown in table 1:
Table 1: performance detection table
| Detection content | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Adhesion strength/MPa | 47.1 | 33.7 | 40.6 | 35.9 | 37.2 |
By 1 testing result of table it is found that present invention gained automotive interior material has excellent adhesive property with composite adhesive.
Claims (10)
1. a kind of preparation method of automotive interior material composite adhesive, it is characterised in that specific preparation process is as follows:
(1) according to parts by weight, by 20~30 parts of rice hull celluloses, 2~3 parts of biogas slurries, 1~2 portion of sucrose, 30~50 parts of water mixing hairs
Ferment filters, freezing, and ball milling is dry, and charing obtains modified fibre；
(2) according to parts by weight, 20~30 parts of isocyanates, 40~60 parts of polyether polyol, 10~20 part of three chloromethane are successively taken
Alkane, 3~5 parts of promotors, 5~8 parts of chlorobenzoyl chlorides, 10~20 parts of modified fibres, 8~10 parts of modified auxiliary materials, 3~5 parts of phosphatide, 3
~5 parts of organic acids, 2~3 parts of plants essential oils, 2~3 parts of greases, 2~3 parts of mica powders；
(3) polyether polyol being placed in reaction kettle, is heated up, vacuum dehydration is cooling, it is subsequently added into isocyanates and promotor,
Constant temperature is stirred to react, and is subsequently added into chloroform, chlorobenzoyl chloride, phosphatide, organic acid, plants essential oil, grease, mica powder, stirring
Mixing discharges to get automotive interior material composite adhesive.
2. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) isocyanates is methyl diphenylene diisocyanate, in toluene di-isocyanate(TDI) or isophorone diisocyanate
Any one.
3. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) polyether polyol is polyoxypropyleneglycol, polyoxytetramethylene glycol or tetrahydrofuran-propylene oxide copolymer glycols
In any one.
4. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) promotor is stannous octoate, any one in isooctyl acid lead or dibutyl tin dilaurate.
5. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) preparation process of the modified auxiliary material are as follows: according to parts by weight, by 8~10 parts of white carbon blacks, 5~8 parts of carbon blacks, 3~5 parts of nitre
Sour silver, 3~5 parts of ammonium chlorides, 30~40 parts of water mixing and ball millings obtain No. 1 mixed liquor, according to parts by weight, by 20~30 parts of propylene
Nitrile, 5~8 parts of azodiisobutyronitriles, 5~8 parts of pentanes, 5~8 parts of methyl methacrylate mixing ultrasounds obtain No. 2 mixed liquors；
No. 2 mixed liquors and No. 1 mixed liquor 1:5~1:10 low-temperature and high-speed in mass ratio are sheared, nitrogen charging high pressure heat-preserving reaction, cooling is let out
Pressure discharges, and filters, and washing obtains modified auxiliary material.
6. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) phosphatide is soybean lecithin, any one in milk phosphatide or yolk phospholipid.
7. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) organic acid is linoleic acid, any one in humic acid or rich dimension acid.
8. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) plants essential oil is Rosemary Oil, Lavender, rose ethereal oil, jasmine essential oil, camellia essential oil or saussurea involucrata essence
Any one in oil.
9. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
(2) grease is in glycerin monostearate, single glyceryl linolenate, bi-tristearin or double glyceryl linolenates
Any one.
10. a kind of preparation method of automotive interior material composite adhesive according to claim 1, it is characterised in that: step
Suddenly (2) described mica powder is any one in white mica powder, black clouds female powder or phlogopite powder.
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Application publication date: 20190802 |