CN106008988A - Preparation method of polypropylene-based modified polyurethane composite material - Google Patents

Preparation method of polypropylene-based modified polyurethane composite material Download PDF

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Publication number
CN106008988A
CN106008988A CN201610476136.9A CN201610476136A CN106008988A CN 106008988 A CN106008988 A CN 106008988A CN 201610476136 A CN201610476136 A CN 201610476136A CN 106008988 A CN106008988 A CN 106008988A
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parts
weight
modified polyurethane
polypropylene
preparation
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Inventor
胡先海
罗俊杰
付昌春
罗辉
王书升
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ANHUI SIWEI NEW BUILDING MATERIAL Co Ltd
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ANHUI SIWEI NEW BUILDING MATERIAL Co Ltd
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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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • C08G18/28—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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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    • 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
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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    • D06M2200/50—Modified hand or grip properties; Softening compositions

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention provides a preparation method of a polypropylene-based modified polyurethane composite material. The preparation method comprises the following operating steps that 1, polyhydric alcohol, diisocyanate, dyhydroxyl carboxylic acid and a chain extender are put into a reaction kettle in a nitrogen atmosphere; 2, the temperature of a polypropylene prepolymer obtained in the step 1 is lowered to below 45 DEG C, and organic amine, a silane coupling agent, deionized water and diamine are added; 3, a water phase and an oil phase are sequentially added into organosilicon-modified polyurethane obtained in the step 2; 4, epoxy resin is added into organosilicon-acrylate-modified polyurethane obtained in the step 3; 5, a product obtained in the step 4 is sprayed on polypropylene non-woven cloth. According to the preparation method, the flexibility and the water resistance of polyurethane are enhanced through organosilicon-modified polyurethane, the mechanical property of polyurethane is enhanced through acrylate-modified polyurethane, the stability and the cohesive property of polyurethane are enhanced through epoxy resin-modified polyurethane, and therefore modified polyurethane which has the water resistance and the high strength and stability is obtained.

Description

A kind of preparation method of polypropylene-base modified polyurethane composite
Technical field
The present invention relates to technical field of macromolecules, particularly relate to the preparation of a kind of polypropylene-base modified polyurethane composite Method.
Background technology
Along with the enhancing of people's environmental consciousness, material safety problem is paid attention to.Polyurethane have do not fire, abnormal smells from the patient is little, nothing The advantage such as malicious, pollution-free, energy-conservation, easy to operate, is the most extensively used as leather finishing agent, textile auxiliary, paper industry auxiliary agent, coating With binding agent etc., its product is successfully applied to the industries such as light textile, leather, timber processing, building, papermaking.Especially at composite Field, can be sprayed on fabric after such as luminescent material, ultraviolet ray-resistant material etc. mix by polyurethane and functional material, thus Obtain function fabric.
But, aqueous polyurethane is adopted and is used water as solvent, the less stable in storage or transportation, easily occurs Lamination, caking property is poor.And, after aqueous polyurethane is combined with base material, owing to the surface tension of WATER AS FLOW MEDIUM is too big, poly- Urethane resistance to water after substrate surface film forming is poor hygroscopic, and film forming fastness is relatively low to be easily separated with base material, and after spraying Product feel harder.
In view of this, it is necessary to polyurethane of the prior art is improved, to solve the problems referred to above.
Summary of the invention
It is an object of the invention to disclose the preparation method of a kind of polypropylene-base modified polyurethane composite, in order to provide A kind of prepare the composite with resistance to water, high-tenacity and high stability.
For achieving the above object, the invention provides the preparation method of a kind of polypropylene-base modified polyurethane composite, Including following operating procedure:
Step one: polyhydric alcohol, diisocyanate, dihydroxy carboxylic acids and chain extender are put into reactor under a nitrogen atmosphere In, reaction temperature is 70 DEG C～90 DEG C, and the response time is 2～4h；Continue to put in a kettle. the double hydroxymethyl propionic acid of 2,2-, third Ketone carries out chain extension end capping reaction, and reaction temperature is 50 DEG C～80 DEG C, and the response time is 2.5～4.5h, prepares base polyurethane prepolymer for use as；
Step 2: the base polyurethane prepolymer for use as obtained in step one is cooled to less than 45 DEG C, there was added under stirring In machine amine with become salt, sequentially add silane coupler, deionized water and diamine, stirring reaction 25～45min, prepare organic Silicon modified polyurethane；
Step 3: sodium lauryl sulphate is dissolved in deionized water as aqueous phase, azodiisobutyronitrile is dissolved in propylene As oil phase in esters of gallic acid monomer, aqueous phase and oil phase are added sequentially in the organic silicon modified polyurethane in step 2, stirring, It is warming up to 70 DEG C～90 DEG C the most under a nitrogen atmosphere, reacts 5～6h, obtain organosilicon/acrylate modified polyurethane；
Step 4: epoxy resin is added in the organosilicon/acrylate modified polyurethane in step 3, stirring, water-bath Heating, reaction temperature is 80 DEG C～90 DEG C, and the response time is 1～2h.
Step 5, is sprayed on the product of step 4 on polypropylene non-woven fabric, and quantity for spray is 240g/m2, pressing 2min, dries Dry；Baking temperature is 60～80 DEG C, and drying time is 5～10min.
The parts by weight of the polyhydric alcohol in described step one are 30～60 parts, the parts by weight of diisocyanate are 5～10 Part, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 40～70 parts and chain extender be 20～40 parts, 2,2-double methylols third The parts by weight of acid are 2～4 parts, the parts by weight of acetone are 20～40 parts；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 30～60 parts, the parts by weight of organic amine be 40～ 70 parts, the parts by weight of silane coupler be 3～4 parts, the weight that parts by weight are 20～50 parts and diamine of deionized water Number is 25～40 parts；
The parts by weight of the sodium lauryl sulphate in described step 3 are 10～20 parts, the parts by weight of deionized water are 30～60, the parts by weight of azodiisobutyronitrile be 6～8 parts, the parts by weight of acrylic ester monomer be 10～30 parts, organic The parts by weight of silicon modified polyurethane are 10～50 parts；
The parts by weight of the epoxy resin in described step 4 are 10～30 parts, organosilicon/acrylate modified polyurethane Parts by weight be 40～60 parts.
In some embodiments, the polyhydric alcohol in described step one is that polyether polyol, PEPA, oligomer are many Unit's alcohol.
In some embodiments, the organic amine in described step 2 is selected from triethylamine or N, N-dimethylethanolamine.
In some embodiments, the silane coupler in described step 2 is selected from KH550, KH602 or KH792.
In some embodiments, the diamine in described step 2 is selected from ethylenediamine, hexamethylene diamine or isophorone diamine.
In some embodiments, the epoxy resin in described step 4 is selected from E-51, E-44, E-42 bisphenol-A epoxy tree Fat.
In some embodiments, the molecular weight of the polyhydric alcohol in described step one is between 1000 to 3000.
In some embodiments, the dihydroxy carboxylic acids in described step one is dihydromethyl propionic acid or dihydroxymethyl fourth Acid.
In some embodiments, the chain extender in described step one is the low-molecular-weight polyhydroxy that molecular weight is less than 400 Compound.
Compared with prior art, the invention has the beneficial effects as follows: changed successively by organosilicon, acrylate and epoxy resin Property polyurethane, organic silicon modified polyurethane adds flexibility and the resistance to water of polyurethane, and polymerization of acrylic modified polyurethane strengthens The mechanical property of polyurethane, epoxy resin modification polyurethane improves stability and the caking property of polyurethane, thus obtains one Plant the modified polyurethane with resistance to water, high-tenacity and high stability, modified polyurethane-coated is obtained on sample Coated product has the features such as soft, resistance to water is strong, adhesive fastness is high, ultimate strength is big.
Detailed description of the invention
The present invention is described in detail for each embodiment shown below, but it should explanation, these embodiments Not limitation of the present invention, those of ordinary skill in the art are according to these embodiment institute work energy, method or structure On equivalent transformation or replacement, within belonging to protection scope of the present invention.
Embodiment one:
A kind of preparation method of organosilicon/acrylate/epoxy resin modification polyurethane, including following operating procedure:
Step one: polyhydric alcohol, diisocyanate, dihydroxy carboxylic acids and chain extender are put into reactor under a nitrogen atmosphere In, reaction temperature is 70 DEG C～90 DEG C, and the response time is 2～4h；Continue to put in a kettle. the double hydroxymethyl propionic acid of 2,2-, third Ketone carries out chain extension end capping reaction, and reaction temperature is 50 DEG C～80 DEG C, and the response time is 2.5～4.5h, prepares base polyurethane prepolymer for use as；
Step 2: the base polyurethane prepolymer for use as obtained in step one is cooled to less than 45 DEG C, there was added under stirring In machine amine with become salt, sequentially add silane coupler, deionized water and diamine, stirring reaction 25～45min, prepare organic Silicon modified polyurethane；
Step 3: sodium lauryl sulphate is dissolved in deionized water as aqueous phase, azodiisobutyronitrile is dissolved in propylene As oil phase in esters of gallic acid monomer, aqueous phase and oil phase are added sequentially in the organic silicon modified polyurethane in step 2, stirring, It is warming up to 70 DEG C～90 DEG C the most under a nitrogen atmosphere, reacts 5～6h, obtain organosilicon/acrylate modified polyurethane；
Step 4: epoxy resin is added in the organosilicon/acrylate modified polyurethane in step 3, stirring, water-bath Heating, reaction temperature is 80 DEG C～90 DEG C, and the response time is 1～2h.
Wherein, the parts by weight of the polyhydric alcohol in step one be 30 parts, the parts by weight of diisocyanate be 5 parts, dihydroxy The parts by weight of yl carboxylic acid be the parts by weight of 40 parts and chain extender be 20 parts, the parts by weight of 2,2-double hydroxymethyl propionic acids are 2 Part, the parts by weight of acetone are 20 parts.
The parts by weight of the base polyurethane prepolymer for use as in step 2 are 30 parts, the parts by weight of organic amine are 40 parts, silane is even The parts by weight that the parts by weight of connection agent are 3 parts, the parts by weight of deionized water are 20 parts and diamine are 25 parts；
The parts by weight of the sodium lauryl sulphate in step 3 are 10 parts, the parts by weight of deionized water are 30, azo The parts by weight of bis-isobutyronitrile are 6 parts, the parts by weight of acrylic ester monomer are 10 parts, the weight of organic silicon modified polyurethane Number is 10 parts；
The parts by weight of the epoxy resin in step 4 are 10 parts, the weight portion of organosilicon/acrylate modified polyurethane Number is 40 parts.
Polyhydric alcohol in step one is polyether polyol, preferably polyoxypropyleneglycol, and dihydroxy carboxylic acids is dihydroxy first Base propanoic acid.Organic amine in step 2 is triethylamine, and silane coupler is KH550, and diamine is ethylenediamine.Step 3 acrylic acid Esters monomer is acrylic acid AA.Epoxy resin in step 4 is E-51 bisphenol A epoxide resin.Dividing of polyhydric alcohol in step one Son amount is between 1000 to 3000, and chain extender is the low-molecular-weight polyhydroxylated compound that molecular weight is less than 400, preferably dihydroxy Base ketone.
Embodiment two:
The present embodiment differs primarily in that with embodiment one:
The parts by weight of the polyhydric alcohol in described step one are 40 parts, the parts by weight of diisocyanate are 6 parts, dihydroxy The parts by weight of carboxylic acid be the parts by weight of 50 parts and chain extender be 25 parts, the parts by weight of 2,2-double hydroxymethyl propionic acids are 2.5 Part, the parts by weight of acetone are 25 parts；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 40 parts, the parts by weight of organic amine are 50 parts, silicon The parts by weight that the parts by weight of alkane coupling agent are 3.5 parts, the parts by weight of deionized water are 30 parts and diamine are 30 parts；
The parts by weight of the sodium lauryl sulphate in described step 3 are 13 parts, the parts by weight of deionized water are 40, The parts by weight of azodiisobutyronitrile are 6.5 parts, the parts by weight of acrylic ester monomer are 15 parts, organic silicon modified polyurethane Parts by weight be 20 parts；
The parts by weight of the epoxy resin in described step 4 are 15 parts, the weight of organosilicon/acrylate modified polyurethane Amount number is 45 parts.
Polyhydric alcohol in step one is polyester diol, and dihydroxy carboxylic acids is dimethylolpropionic acid.Organic in step 2 Amine is N, N-dimethylethanolamine, and silane coupler is selected from KH602, and diamine is hexamethylene diamine.Epoxy resin in step 4 is E-44 bisphenol A epoxide resin.Step 3 acrylic ester monomer is acrylic acid methyl ester. MA.
Embodiment three:
The present embodiment differs primarily in that with embodiment one:
The parts by weight of the polyhydric alcohol in step one are 50 parts, the parts by weight of diisocyanate are 9 parts, dihydroxy carboxylic acids The parts by weight that parts by weight are 60 parts and chain extender be 35 parts, the parts by weight of 2,2-double hydroxymethyl propionic acids are 3 parts, acetone Parts by weight be 35 parts；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 50 parts, the parts by weight of organic amine are 60 parts, silicon The parts by weight that the parts by weight of alkane coupling agent are 3.8 parts, the parts by weight of deionized water are 40 parts and diamine are 35 parts；
The parts by weight of the sodium lauryl sulphate in described step 3 are 18 parts, the parts by weight of deionized water are 50, The parts by weight of azodiisobutyronitrile are 7.5 parts, the parts by weight of acrylic ester monomer are 25 parts, organic silicon modified polyurethane Parts by weight be 40 parts；
The parts by weight of the epoxy resin in described step 4 are 25 parts, the weight of organosilicon/acrylate modified polyurethane Amount number is 55 parts.
Polyhydric alcohol in step one is polyester diol.Silane coupler in step 2 is selected from KH792, and diamine is selected from Isophorone diamine.Epoxy resin in step 4 is selected from E-42 bisphenol A epoxide resin.
Embodiment four:
The present embodiment differs primarily in that with above-described embodiment:
The parts by weight of the polyhydric alcohol in described step one are 60 parts, the parts by weight of diisocyanate are 10 parts, dihydroxy The parts by weight of yl carboxylic acid be the parts by weight of 70 parts and chain extender be 40 parts, the parts by weight of 2,2-double hydroxymethyl propionic acids are 4 Part, the parts by weight of acetone are 40 parts；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 60 parts, the parts by weight of organic amine are 70 parts, silicon The parts by weight that the parts by weight of alkane coupling agent are 4 parts, the parts by weight of deionized water are 50 parts and diamine are 40 parts；
The parts by weight of the sodium lauryl sulphate in described step 3 are 20 parts, the parts by weight of deionized water are 60, The parts by weight of azodiisobutyronitrile are 8 parts, the parts by weight of acrylic ester monomer are 30 parts, organic silicon modified polyurethane Parts by weight are 50 parts；
The parts by weight of the epoxy resin in described step 4 are 30 parts, the weight of organosilicon/acrylate modified polyurethane Amount number is 60 parts.
Polypropylene-base modified polyurethane composite embodiment 1-4 obtained carries out performance test, and wherein, matched group is Without the polyurethane of organosilicon/acrylate/epoxy resin modification, test result is as shown in table 1:
Modified polyurethane embodiment 1-4 obtained is sprayed on sample respectively, and quantity for spray is 240g/m2, pressing 2min, Baking temperature is 60～80 DEG C, and drying time is 5～10min.Test after 48 hours.Wherein, sample can be knitted fabric, machine Fabric or non-woven fabrics.The present invention preferably uses polypropylene non-woven fabric.Matched group is without surveying organosilicon/acrylate/asphalt mixtures modified by epoxy resin The sample of the polyurethane coating that fat is modified, test result is as shown in table 2.
As can be seen from Table 1 and Table 2, compared with the polyurethane of non-modified, through organosilicon, acrylate, asphalt mixtures modified by epoxy resin The most modified polyurethane of fat has preferable flexibility, resistance to water, mechanical property, stability and caking property.By polypropylene After base modified polyurethane composite is coated on the samples such as knitted fabric, woven fabric or non-woven fabrics, the sample after coating each Planting performance to be improved relative to the sample coating unmodified polyurethane, specifically, the feel of coated product is more soft, resistance to Aqueous energy is higher, ultimate strength increases, adhesive fastness is more preferable.
The a series of detailed description of those listed above is only for the feasibility embodiment of the present invention specifically Bright, they also are not used to limit the scope of the invention, all equivalent implementations made without departing from skill of the present invention spirit Or change should be included within the scope of the present invention.
Although moreover, it will be appreciated that this specification is been described by according to embodiment, but the most each embodiment only wraps Containing an independent technical scheme, this narrating mode of description is only that for clarity sake those skilled in the art should Description can also be formed those skilled in the art through appropriately combined as an entirety, the technical scheme in each embodiment May be appreciated other embodiments.

Claims (9)

1. the preparation method of a polypropylene-base modified polyurethane composite, it is characterised in that include following operating procedure:
Step one: polyhydric alcohol, diisocyanate, dihydroxy carboxylic acids and chain extender are put in reactor under a nitrogen atmosphere, instead Answering temperature is 70 DEG C～90 DEG C, and the response time is 2～4h；Continue to put into the double hydroxymethyl propionic acid of 2,2-in a kettle., acetone enters Row chain extension end capping reaction, reaction temperature is 50 DEG C～80 DEG C, and the response time is 2.5～4.5h, prepares base polyurethane prepolymer for use as；
The parts by weight of the polyhydric alcohol in described step one are 30～60 parts, the parts by weight of diisocyanate are 5～10 parts, two The parts by weight of hydroxy carboxylic acid be the parts by weight of 40～70 parts and chain extender be 20～40 parts, the weight of 2,2-double hydroxymethyl propionic acids Amount number is 2～4 parts, the parts by weight of acetone are 20～40 parts；
Step 2: the base polyurethane prepolymer for use as obtained in step one is cooled to less than 45 DEG C, adds organic amine under stirring Neutralizing into salt, sequentially add silane coupler, deionized water and diamine, stirring reaction 25～45min, prepared organosilicon changes Property polyurethane；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 30～60 parts, the parts by weight of organic amine are 40～70 Part, the parts by weight of silane coupler are 3～4 parts, the weight portion that parts by weight are 20～50 parts and diamine of deionized water Number is 25～40 parts；
Step 3: sodium lauryl sulphate is dissolved in deionized water as aqueous phase, azodiisobutyronitrile is dissolved in acrylate As oil phase in class monomer, aqueous phase and oil phase are added sequentially in the organic silicon modified polyurethane in step 2, stirring, then It is warming up to 70 DEG C～90 DEG C under a nitrogen atmosphere, reacts 5～6h, obtain organosilicon/acrylate modified polyurethane；
The parts by weight of the sodium lauryl sulphate in described step 3 are 10～20 parts, the parts by weight of deionized water be 30～ 60, the parts by weight of azodiisobutyronitrile be 6～8 parts, the parts by weight of acrylic ester monomer be 10～30 parts, organosilicon changes The parts by weight of property polyurethane are 10～50 parts；
Step 4: epoxy resin is added in the organosilicon/acrylate modified polyurethane in step 3, stirring, heating in water bath, Reaction temperature is 80 DEG C～90 DEG C, and the response time is 1～2h；
The parts by weight of the epoxy resin in described step 4 are 10～30 parts, the weight of organosilicon/acrylate modified polyurethane Amount number is 40～60 parts；
Step 5, is sprayed on the product of step 4 on polypropylene non-woven fabric, and quantity for spray is 240g/m2, pressing 2min, dry；Dry Dry temperature is 60～80 DEG C, and drying time is 5～10min.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described Polyhydric alcohol in step one is polyether polyol or PEPA or oligomer polyol.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described Organic amine in step 2 is selected from triethylamine or N, N-dimethylethanolamine.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described Silane coupler in step 2 is selected from KH550 or KH602 or KH792.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described Diamine in step 2 is selected from ethylenediamine or hexamethylene diamine or isophorone diamine.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described Epoxy resin in step 4 is selected from E-51 or E-44 or E-42 bisphenol A epoxide resin.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described The molecular weight of the polyhydric alcohol in step one is between 1000 to 3000.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described Dihydroxy carboxylic acids in step one is dihydromethyl propionic acid or dimethylolpropionic acid.
The preparation method of polypropylene-base modified polyurethane composite the most according to claim 1, it is characterised in that described Chain extender in step one is the low-molecular-weight polyhydroxylated compound that molecular weight is less than 400.
CN201610476136.9A 2016-06-24 2016-06-24 Preparation method of polypropylene-based modified polyurethane composite material Pending CN106008988A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976354A (en) * 2018-07-16 2018-12-11 黄山泰尔新材料有限公司 A kind of environmentally friendly type polyurethane complex thickener and preparation method thereof of associating
CN112250827A (en) * 2020-09-23 2021-01-22 苏州联胜化学有限公司 Multipurpose wet rubbing fastness improver and preparation method thereof
CN117531469A (en) * 2023-10-16 2024-02-09 南雄市沃太化工有限公司 Waterproof polyurethane acrylate composite material and preparation device thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408537A (en) * 2011-09-19 2012-04-11 福建宝利特新材料科技有限公司 Preparation method of acrylate modified water-borne polyurethane emulsion for synthetic leather
CN105218752A (en) * 2015-09-14 2016-01-06 江苏龙昇高分子材料科技有限公司 The preparation method of the polyurethane-acrylate water dispersion of epoxy-silicone resin modification and water-based epoxy zinc-rich primer
CN105461863A (en) * 2015-12-23 2016-04-06 中山大学惠州研究院 Acrylate modified waterborne polyurethane emulsion and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408537A (en) * 2011-09-19 2012-04-11 福建宝利特新材料科技有限公司 Preparation method of acrylate modified water-borne polyurethane emulsion for synthetic leather
CN105218752A (en) * 2015-09-14 2016-01-06 江苏龙昇高分子材料科技有限公司 The preparation method of the polyurethane-acrylate water dispersion of epoxy-silicone resin modification and water-based epoxy zinc-rich primer
CN105461863A (en) * 2015-12-23 2016-04-06 中山大学惠州研究院 Acrylate modified waterborne polyurethane emulsion and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976354A (en) * 2018-07-16 2018-12-11 黄山泰尔新材料有限公司 A kind of environmentally friendly type polyurethane complex thickener and preparation method thereof of associating
CN112250827A (en) * 2020-09-23 2021-01-22 苏州联胜化学有限公司 Multipurpose wet rubbing fastness improver and preparation method thereof
CN112250827B (en) * 2020-09-23 2022-07-26 苏州联胜化学有限公司 Multipurpose wet rubbing fastness improver and preparation method thereof
CN117531469A (en) * 2023-10-16 2024-02-09 南雄市沃太化工有限公司 Waterproof polyurethane acrylate composite material and preparation device thereof
CN117531469B (en) * 2023-10-16 2024-06-11 南雄市沃太化工有限公司 Waterproof polyurethane acrylate composite material and preparation device thereof

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Application publication date: 20161012