CN105859977A - Preparation method of organosilicon/acrylic ester/epoxy resin modified polyurethane - Google Patents
Preparation method of organosilicon/acrylic ester/epoxy resin modified polyurethane Download PDFInfo
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- 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
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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
- C08G18/08—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- 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
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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
- C08G18/58—Epoxy resins
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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
- C08G18/65—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
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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
- C08G18/65—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
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of organosilicon/acrylic ester/epoxy resin modified polyurethane. The preparation method includes the steps of firstly, placing polyol, diisocyanate, dyhydroxyl carboxylic acid and chain extender into a reaction kettle under nitrogen atmosphere; secondly, cooling the polyurethane prepolymer obtained in the first step to below 45 DEG C, adding organic amine, silane coupling agent, deionized water and diamine; thirdly, sequentially adding water phase and oil phase into the organosilicon modified polyurethane obtained in the second step; fourthly, adding epoxy resin into the organosilicon/acrylic ester modified polyurethane obtained in the third step. The preparation method has the advantages that the polyurethane is sequentially modified by the organosilicon, the acrylic ester and the epoxy resin, the softness and water resistance of the polyurethane are increased when the polyurethane is modified by the organosilicon, the mechanical performance of the polyurethane is enhanced when the polyurethane is modified by the acrylic ester, the stability and cohesiveness of the polyurethane are increased when the polyurethane is modified by the epoxy resin, and the modified polyurethane with high water resistance, high mechanical performance and high stability is obtained.
Description
Technical field
The present invention relates to technical field of macromolecules, particularly relate to a kind of organosilicon/acrylate/epoxy resin
The preparation method of modified polyurethane.
Background technology
Along with the enhancing of people's environmental consciousness, material safety problem is paid attention to.Polyurethane have do not fire,
The advantages such as smell is little, nontoxic, pollution-free, energy-conservation, easy to operate, be the most extensively used as leather finishing agent,
Textile auxiliary, paper industry auxiliary agent, coating and adhesive etc., its product is successfully applied to light textile, skin
The industries such as leather, timber processing, building, papermaking.Especially in field of compound material, polyurethane can be passed through
Spray on fabric after such as luminescent material, ultraviolet ray-resistant material etc. mix with functional material, thus obtain
Obtain function fabric.
But, aqueous polyurethane is adopted and is used water as solvent, the stability in storage or transportation
Poor, lamination easily occurs, 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, the poor easy suction of polyurethane resistance to water after substrate surface film forming
Water, film forming fastness is relatively low to be easily separated with base material, and the product feel after spraying is harder.
In view of this, it is necessary to polyurethane of the prior art is improved, to solve above-mentioned asking
Topic.
Summary of the invention
It is an object of the invention to disclose a kind of organosilicon/acrylate/epoxy resin modification polyurethane
Preparation method, in order to provide have the modified polyurethane of resistance to water, high-tenacity and high stability a kind of preparation
Method.
For achieving the above object, the invention provides a kind of organosilicon/acrylate/epoxy resin modification to gather
The preparation method of urethane, including following operating procedure:
Step one: polyalcohol, diisocyanate, dihydroxy carboxylic acids and chain extender are put under a nitrogen atmosphere
Entering in reactor, reaction temperature is 70 DEG C～90 DEG C, and the reaction time is 2～4h；Continue to put in a kettle.
Entering 2, the double hydroxymethyl propionic acid of 2-, acetone carry out chain extension end capping reaction, and reaction temperature is 50 DEG C～80 DEG C, instead
It is 2.5～4.5h between Ying Shi, 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, at stirring
In lower addition organic amine with become salt, sequentially add silane coupler, deionized water and diamine, stirring
Reaction 25～45min, prepares organic silicon modified polyurethane；
Step 3: lauryl sodium sulfate is dissolved in deionized water as aqueous phase, by azodiisobutyronitrile
Being dissolved in acrylic ester monomer as oil phase, aqueous phase and oil phase are added sequentially in step 2 is organic
In silicon modified polyurethane, 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, stir
Mixing, heating water bath, reaction temperature is 80 DEG C～90 DEG C, and the reaction time is 1～2h.
The parts by weight of the polyalcohol in described step one are 30～60 parts, the parts by weight of diisocyanate
Be 5～10 parts, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 40～70 parts and chain extender be 20～40
Part, the parts by weight of 2,2-double hydroxymethyl propionic acids 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 weight portion of organic amine
Number is 40～70 parts, the parts by weight of silane coupler are 3～4 parts, the parts by weight of deionized water are
20～50 parts is 25～40 parts with the parts by weight of diamine；
The parts by weight of the lauryl sodium sulfate in described step 3 are 10～20 parts, the weight of deionized water
Amount number is 30～60, the parts by weight of azodiisobutyronitrile are 6～8 parts, the weight of acrylic ester monomer
Amount number is 10～30 parts, the parts by weight of organic silicon modified polyurethane are 10～50 parts；
The parts by weight of the epoxy resin in described step 4 are 10～30 parts, and organosilicon/acrylate is modified
The parts by weight of polyurethane are 40～60 parts.
In some embodiments, the polyalcohol in described step one be PPG, PEPA,
Oligomer polyol.
In some embodiments, the organic amine in described step 2 is selected from triethylamine or N, N-dimethyl
Monoethanolamine.
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 different Buddhist
That ketone diamines.
In some embodiments, the epoxy resin in described step 4 is selected from E-51, E-44, E-42
Bisphenol A epoxide resin.
In some embodiments, the molecular weight of the polyalcohol in described step one is between 1000 to 3000
Between.
In some embodiments, the dihydroxy carboxylic acids in described step one is dihydromethyl propionic acid or dihydroxy
Methylbutanoic acid.
In some embodiments, the chain extender in described step one is the low molecule that molecular weight is less than 400
Amount polyol.
Compared with prior art, the invention has the beneficial effects as follows: by organosilicon, acrylate and ring
Epoxy resins modified polyurethane successively, organic silicon modified polyurethane adds the flexibility of polyurethane and water-fast
Property, polymerization of acrylic modified polyurethane enhances the mechanical property of polyurethane, epoxy resin modification polyurethane
Improve stability and the caking property of polyurethane, thus obtain one and there is resistance to water, high-tenacity and height
The modified polyurethane of stability, the coated product modified polyurethane-coated obtained on sample has
There are 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
Embodiment not limitation of the present invention, those of ordinary skill in the art are made according to these embodiments
Function, method or structure on equivalent transformation or replacement, belong to protection scope of the present invention it
In.
Embodiment one:
The preparation method of a kind of organosilicon/acrylate/epoxy resin modification polyurethane, including operating as follows
Step:
Step one: polyalcohol, diisocyanate, dihydroxy carboxylic acids and chain extender are put under a nitrogen atmosphere
Entering in reactor, reaction temperature is 70 DEG C～90 DEG C, and the reaction time is 2～4h；Continue to put in a kettle.
Entering 2, the double hydroxymethyl propionic acid of 2-, acetone carry out chain extension end capping reaction, and reaction temperature is 50 DEG C～80 DEG C, instead
It is 2.5～4.5h between Ying Shi, 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, at stirring
In lower addition organic amine with become salt, sequentially add silane coupler, deionized water and diamine, stirring
Reaction 25～45min, prepares organic silicon modified polyurethane；
Step 3: lauryl sodium sulfate is dissolved in deionized water as aqueous phase, by azodiisobutyronitrile
Being dissolved in acrylic ester monomer as oil phase, aqueous phase and oil phase are added sequentially in step 2 is organic
In silicon modified polyurethane, 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, stir
Mixing, heating water bath, reaction temperature is 80 DEG C～90 DEG C, and the reaction time is 1～2h.
Wherein, the parts by weight of the polyalcohol in step one are 30 parts, the parts by weight of diisocyanate
Be 5 parts, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 40 parts and chain extender be 20 parts, 2,2-
The parts by weight of double hydroxymethyl propionic acids are 2 parts, 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
Part, the parts by weight of silane coupler be 3 parts, the parts by weight of deionized water be 20 parts and diamine
Parts by weight be 25 parts；
The parts by weight of the lauryl sodium sulfate in step 3 are 10 parts, the parts by weight of deionized water
Be 30, the parts by weight of azodiisobutyronitrile be 6 parts, the parts by weight of acrylic ester monomer be 10
Part, the parts by weight of organic silicon modified polyurethane are 10 parts；
The parts by weight of the epoxy resin in step 4 are 10 parts, organosilicon/acrylate modified polyurethane
Parts by weight be 40 parts.
Polyalcohol in step one is PPG, preferably polyoxypropyleneglycol, dihydroxy carboxylic acids
For dihydromethyl propionic acid.Organic amine in step 2 is triethylamine, and silane coupler is KH550, binary
Amine is ethylenediamine.Step 3 acrylic ester monomer is acrylic acid AA.Epoxy resin in step 4 is
E-51 bisphenol A epoxide resin.The molecular weight of the polyalcohol in step one between 1000 to 3000,
Chain extender is the low-molecular-weight polyhydroxylated compound that molecular weight is less than 400, preferably dihydroxy ketone.
Embodiment two:
The present embodiment differs primarily in that with embodiment one:
The parts by weight of the polyalcohol in described step one are 40 parts, the parts by weight of diisocyanate are 6
Part, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 50 parts and chain extender be 25 parts, 2,2-double hydroxyls
The parts by weight of methylpropanoic acid are 2.5 parts, 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
Be 50 parts, the parts by weight of silane coupler be 3.5 parts, the parts by weight of deionized water be 30 parts and
The parts by weight of diamine are 30 parts；
The parts by weight of the lauryl sodium sulfate in described step 3 are 13 parts, the weight of deionized water
Number is 40, the parts by weight of azodiisobutyronitrile are 6.5 parts, the parts by weight of acrylic ester monomer
Be 15 parts, the parts by weight of organic silicon modified polyurethane be 20 parts；
The parts by weight of the epoxy resin in described step 4 are 15 parts, and organosilicon/acrylate modification gathers
The parts by weight of urethane are 45 parts.
Polyalcohol in step one is polyester diol, and dihydroxy carboxylic acids is dimethylolpropionic acid.Step 2
In organic amine be N, N-dimethylethanolamine, silane coupler be selected from KH602, diamine be oneself two
Amine.Epoxy resin in step 4 is E-44 bisphenol A epoxide resin.Step 3 acrylic ester monomer
For methyl acrylate MA.
Embodiment three:
The present embodiment differs primarily in that with embodiment one:
The parts by weight of the polyalcohol in step one are 50 parts, the parts by weight of diisocyanate are 9 parts,
The parts by weight of dihydroxy carboxylic acids be the parts by weight of 60 parts and chain extender be 35 parts, 2,2-double methylols
The parts by weight of propionic acid are 3 parts, the parts by weight of acetone are 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
Be 60 parts, the parts by weight of silane coupler be 3.8 parts, the parts by weight of deionized water be 40 parts and
The parts by weight of diamine are 35 parts；
The parts by weight of the lauryl sodium sulfate in described step 3 are 18 parts, the weight of deionized water
Number is 50, the parts by weight of azodiisobutyronitrile are 7.5 parts, the parts by weight of acrylic ester monomer
Be 25 parts, the parts by weight of organic silicon modified polyurethane be 40 parts；
The parts by weight of the epoxy resin in described step 4 are 25 parts, and organosilicon/acrylate modification gathers
The parts by weight of urethane are 55 parts.
Polyalcohol in step one is polyester diol.Silane coupler in step 2 is selected from KH792,
Diamine is selected from IPD.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 polyalcohol in described step one are 60 parts, the parts by weight of diisocyanate are
10 parts, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 70 parts and chain extender be 40 parts, 2,2-is double
The parts by weight of hydroxymethyl propionic acid are 4 parts, 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
Be 70 parts, the parts by weight of silane coupler be 4 parts, the parts by weight of deionized water be 50 parts and two
The parts by weight of unit's amine are 40 parts；
The parts by weight of the lauryl sodium sulfate in described step 3 are 20 parts, the weight of deionized water
Number is 60, the parts by weight of azodiisobutyronitrile are 8 parts, the parts by weight of acrylic ester monomer are
30 parts, the parts by weight of organic silicon modified polyurethane be 50 parts；
The parts by weight of the epoxy resin in described step 4 are 30 parts, and organosilicon/acrylate modification gathers
The parts by weight of urethane are 60 parts.
Organosilicon/acrylate embodiment 1-4 obtained/epoxy resin modification polyurethane carries out performance
Test, wherein, control group is the polyurethane without organosilicon/acrylate/epoxy resin modification, examination knot
Fruit is as shown in table 1:
Organosilicon/acrylate embodiment 1-4 obtained/epoxy resin modification polyurethane is sprayed on respectively
On sample, quantity for spray is 240g/m2, pressing 2min, tested after 48 hours.Wherein, sample
Can be knitted fabric, woven fabric or non-woven fabrics, control group be 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, propylene
The most modified polyurethane of acid esters, epoxy resin have preferable flexibility, resistance to water, mechanical property,
Stability and caking property.By organosilicon/acrylate/epoxy resin modification polyurethane-coated knitted fabric,
After on the sample such as woven fabric or non-woven fabrics, the various performances of the sample after coating are unmodified relative to coating
The sample of polyurethane improved, specifically, the feel of coated product is more soft, and water resistance is more
By force, ultimate strength increase, adhesive fastness more preferable.
The a series of detailed description of those listed above is only for the feasibility embodiment of the present invention
Illustrate, they also are not used to limit the scope of the invention, all without departing from skill of the present invention essence
Equivalent implementations or change that god is made should be included within the scope of the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, but the most each reality
Mode of executing only comprises an independent technical scheme, and this narrating mode of specification is only for understand
Seeing, those skilled in the art should be using specification as an entirety, and the technical scheme in each embodiment is also
Other embodiments that it will be appreciated by those skilled in the art that can be formed through appropriately combined.
Claims (9)
1. the preparation method of organosilicon/acrylate/epoxy resin modification polyurethane, it is characterised in that
Including following operating procedure:
Step one: polyalcohol, diisocyanate, dihydroxy carboxylic acids and chain extender are put under a nitrogen atmosphere
Entering in reactor, reaction temperature is 70 DEG C～90 DEG C, and the reaction time is 2～4h；Continue to put in a kettle.
Entering 2, the double hydroxymethyl propionic acid of 2-, acetone carry out chain extension end capping reaction, and reaction temperature is 50 DEG C～80 DEG C, instead
It is 2.5～4.5h between Ying Shi, prepares base polyurethane prepolymer for use as；
The parts by weight of the polyalcohol in described step one are 30～60 parts, the parts by weight of diisocyanate
Be 5～10 parts, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 40～70 parts and chain extender be 20～40
Part, the parts by weight of 2,2-double hydroxymethyl propionic acids are 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, at stirring
In lower addition organic amine with become salt, sequentially add silane coupler, deionized water and diamine, stirring
Reaction 25～45min, prepares organic silicon modified polyurethane；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 30～60 parts, the weight portion of organic amine
Number is 40～70 parts, the parts by weight of silane coupler are 3～4 parts, the parts by weight of deionized water are
20～50 parts is 25～40 parts with the parts by weight of diamine；
Step 3: lauryl sodium sulfate is dissolved in deionized water as aqueous phase, by azodiisobutyronitrile
Being dissolved in acrylic ester monomer as oil phase, aqueous phase and oil phase are added sequentially in step 2 is organic
In silicon modified polyurethane, 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；
The parts by weight of the lauryl sodium sulfate in described step 3 are 10～20 parts, the weight of deionized water
Amount number is 30～60, the parts by weight of azodiisobutyronitrile are 6～8 parts, the weight of acrylic ester monomer
Amount number is 10～30 parts, the parts by weight of organic silicon modified polyurethane are 10～50 parts；
Step 4: epoxy resin is added in the organosilicon/acrylate modified polyurethane in step 3, stir
Mixing, heating water bath, reaction temperature is 80 DEG C～90 DEG C, and the reaction time is 1～2h；
The parts by weight of the epoxy resin in described step 4 are 10～30 parts, and organosilicon/acrylate is modified
The parts by weight of polyurethane are 40～60 parts.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the polyalcohol in described step one is PPG or PEPA or low
Polymers polyalcohol.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the organic amine in described step 2 is selected from triethylamine or N, N-dimethyl ethanol
Amine.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the silane coupler in described step 2 selected from KH550 or KH602 or
KH792。
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the diamine in described step 2 is selected from ethylenediamine or hexamethylene diamine or isophorone
Diamines.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the epoxy resin in described step 4 is selected from E-51 or E-44 or E-42 bis-phenol
A epoxy resin.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the molecular weight of the polyalcohol in described step one is between 1000 to 3000.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the dihydroxy carboxylic acids in described step one is dihydromethyl propionic acid or dihydroxymethyl
Butyric acid.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the chain extender in described step one be molecular weight be less than 400 low-molecular-weight many
Hydroxy compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610476089.8A CN105859977B (en) | 2016-06-24 | 2016-06-24 | A kind of preparation method of organosilicon/acrylate/epoxy resin modification polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610476089.8A CN105859977B (en) | 2016-06-24 | 2016-06-24 | A kind of preparation method of organosilicon/acrylate/epoxy resin modification polyurethane |
Publications (2)
| Publication Number | Publication Date |
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| CN105859977A true CN105859977A (en) | 2016-08-17 |
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| CN106939063A (en) * | 2017-04-01 | 2017-07-11 | 武汉理工大学 | A kind of organic silicon modified polyurethane/epoxy/acrylic acid ester composite emulsion and preparation method thereof |
| CN111440285A (en) * | 2020-01-20 | 2020-07-24 | 长安大学 | Preparation method of organic silicon/polyurethane/bismaleimide modified epoxy resin |
| 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 |
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| CN106939063A (en) * | 2017-04-01 | 2017-07-11 | 武汉理工大学 | A kind of organic silicon modified polyurethane/epoxy/acrylic acid ester composite emulsion and preparation method thereof |
| CN106939063B (en) * | 2017-04-01 | 2019-09-10 | 武汉理工大学 | A kind of organic silicon modified polyurethane/epoxy/acrylic acid ester composite emulsion and preparation method thereof |
| CN111440285A (en) * | 2020-01-20 | 2020-07-24 | 长安大学 | Preparation method of organic silicon/polyurethane/bismaleimide modified epoxy resin |
| 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 |
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