CN104672399A - Novel method for preparing crylic acid modified resin for two-component waterborne polyurethane adhesive - Google Patents
Novel method for preparing crylic acid modified resin for two-component waterborne polyurethane adhesive Download PDFInfo
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Abstract
The invention belongs to the field of adhesives, and discloses a novel method for preparing crylic acid modified resin for a two-component waterborne polyurethane adhesive. The novel method comprises the following steps: directly selecting polymer resin or synthesizing polymer resin from raw materials, adding a solvent into the polymer resin or synthesizing polymer resin from raw material, thereby modifying by using vinyl or crylic acid and an ester monomer at certain temperature or in the presence of an initiator, and further implementing a reaction on organic amino and acid substances, thereby obtaining the crylic acid modified resin for the two-component waterborne polyurethane adhesive. By adopting the method, crylic acid modified resin can be prepared, and can be directly used or is combined with a component containing isocyanate to obtain a polyurethane adhesive after chain expansion, the isocyanate group in the adhesive can be preferably reacted with active groups of resin in a waterborne environment, and can stably exist in the waterborne environment; in addition, compared with a solvent type polyurethane adhesive, the adhesive is relatively low in VOC content, the defects that an ordinary waterborne polyurethane adhesive can be stripped from a substrate, has bubbles in an adhesive film, is poor in adhesion and has material defects after being used can be avoided, and the cost of the polyurethane adhesive can be lowered.
Description
Technical field
The present invention relates to a kind of novel aqueous two-component polyurethane adhesive and stick the preparation method of agent with acrylic acid modified resin, belong to sizing agent field.
Background technology
Adhesive for polyurethane refers to the sizing agent containing ammonia ester bond or isocyanate group in base-material molecule.Containing very strong polarity and the vivaciously a little isocyanate group of chemistry and urethano in adhesive for polyurethane, have excellent chemical adhesion with the smooth finish surface material such as porous material and metal, glass, rubber, plastics such as the material containing reactive hydrogen, timber, leather, paper, pottery, bonding firmly.Because isocyanate groups is very active, can with the compound containing reactive hydrogen as alcohol, acid, amine and water react, and react according to certain equivalent, the reaction of isocyanic ester and water generates carbonic acid gas, cause the loss of isocyanic ester, thus cause reducing with the isocyanic ester that reacts in base material or sizing agent base-material, adhesive property is caused to decline even failed, so moisture and the material containing the reactive hydrogen content as alcohols amine and phenols strictly will be controlled in the various raw material of general adhesive for polyurethane and thinner, at high humidity weather as southern plum rain season often causes the fluctuation of adhesive property, cause unnecessary loss.
And at present domestic adhesive for polyurethane be mainly Solvent type double-component polyurethane adhesive, containing a large amount of ester classes, ketone, benzene class and free isocyanate, hinder HUMAN HEALTH, destroy ecotope.In order to avoid the volatilization of a large amount of organic solvent, scientific research personnel have developed aqueous polyurethane coating; General aqueous polyurethane greatly reduces the content of VOC, but due to the instability of performance, isocyanic ester can react with water and produce carbon dioxide, and constructing operation easily causes gel accidentally, peels off with base material, play the disadvantages such as vesicle.And aqueous double-component polyurethane sizing agent price is higher, so aqueous double-component polyurethane sizing agent has certain limitation in the application at present.
Summary of the invention
The present invention has prepared a kind of aqueous acrylic modified resin and adhesive for polyurethane that can be used for aqueous double-component polyurethane sizing agent, this resin can using water as thinner, coordinate with containing isocyanate curing agent component during use and be mixed with Aqueous Polyurethane Adhesives, not only lower than common solvent type polyurethane sizing agent VOC content; Also solve the disadvantage such as base material stripping, foaming that general aqueous double-component polyurethane sizing agent easily occurs when boning; And also reduce the cost of aqueous double-component polyurethane sizing agent.
A kind of aqueous double-component polyurethane sizing agent, by A, B component is formed, component A is acrylic acid modified resin, the molecular weight ranges of resin is 1600-30000, preferable range is 2000-16000, can dilute with water or organic solvent, B component is for containing polyisocyanate species, comprise TDI, MDI, HDI, the isocyanic ester such as PAPI, the reaction product of itself and many hydroxymethyl-propanes (or glycerine) and dimer tripolymer polymer thereof, this component uses as the solidifying agent of reaction, can carry out being diluted to concentration with a certain proportion of organic solvent is before use 60%-80%.
Component A is acrylic acid modified resin, is synthesized by the raw material reaction of following weight percentage: 0-80 part macromolecule resin, 0-60 part solvent, 10-90 part vinyl or acrylicacidandesters class monomer, 0-8 part initiator, 0.1-20 part organic amine, 0-20 part acid.
The preferred version of the various raw materials in formula is: 0-50 part macromolecule resin, 10-60 part solvent, 20-80 part vinyl or acrylicacidandesters class monomer, 0.1-8 part initiator, 0.1-10 part organic amine, 0.1-10 part acid.
Macromolecule resin is selected from one or more in vibrin, Synolac, epoxy resin, resol.
Macromolecule resin is selected from polyester or Synolac, the monomer selected in its building-up process comprises: hexanodioic acid, MALEIC ANHYDRIDE, terephthalic acid, m-phthalic acid, trimellitic acid 1,2-anhydride, one or more in TriMethylolPropane(TMP), neopentyl glycol, dimethylol propionic acid, ricinolic acid, behenic acid, cocinic acid, synthetic fatty acid.
Described solvent is selected from ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, butanols or alcohol ester 12, N-Methyl pyrrolidone, one or more in butyl.
Described vinyl or acrylicacidandesters class monomer are selected from one or more in vinylbenzene, vinylformic acid, methacrylic acid, butyl methacrylate, methyl methacrylate, butyl acrylate, (methyl) glycidyl acrylate, 1,2-epoxy-4-vinyl cyclohexane, lauryl methacrylate(LMA), isobornyl methacrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate.
Described initiator is selected from dibenzoyl peroxide, peroxidized t-butyl perbenzoate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), cyclohexanone peroxide, tertbutyl peroxide, dicumyl peroxide, hydrogen peroxide, persulphate, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride, 2,2 '-azo two (2-methyl-4-carboxyl butyronitrile), 2, one or more in 2 '-azo two (2-cyanogen propane-1-sulfonate).
Described organic amine is one or more in diethylenetriamine, triethylene tetramine, monomethyl-ethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol.
Described acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, tetra-sodium, polyphosphoric acid, citric acid, formic acid, acetic acid, lactic acid.
Two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin, comprises the following steps:
(1) interpolation or synthetic macromolecule resin 0-80 weight part, add in reactor by polyprotonic acid and polyvalent alcohol, heats up, still temperature 160-240 DEG C, column temperature 90-100 DEG C, and reaction water outlet, measures the water yield, controls acid number and be less than 5mgKOH/g.
(2) by the solvent of 0-60 weight part, add in there-necked flask, be warming up to 60 DEG C-150 DEG C;
(3) drip the mixture of 10-90 part vinyl or acrylicacidandesters class and initiator under stirring state at 60-150 DEG C, 2-6hr dropwises, and dropwises rear 60-150 DEG C of insulation 2-4hr.
(4) be cooled to 50-90 DEG C, add 0.1-20 part organic amine, under the state stirred, insulation 0.5-3hr;
(5) add 0-20 part acid under heat-retaining condition, namely stirring 0.5-2hr obtains two-component polyurethane adhesive and sticks the acrylic acid modified resin of agent.
Obtained resin is got 0.9-0.99 according to the amount of substance of isocyanic ester/hydroxyl, and add the glycerol/ethylene glycol of 0-0.15, add the isocyanic ester such as TDI, MDI, HDI, PAPI and carry out backflow chain extending reaction 3-5hr at 80-105 DEG C, obtain component A, also can with obtained acrylic acid modified resin directly as component A.
B component is polyisocyanate curing agent.Alternative polyisocyanate curing agent comprises: the material of the polyisocynate monomers such as TDI, HDI, MDI, IPDI and dimer, tripolymer and polymer and above-mentioned uretdione, tripolymer and many hydroxymethyl-propanes (as TriMethylolPropane(TMP), glycerine etc.) reaction generation.
The invention has the beneficial effects as follows: the aqueous acrylic modified resin as one of main film forming substance can use with solvent-borne type isocyanic ester compatibility, solvent-borne type isocyanic ester is dispersed in water, but do not form bubble with a large amount of generated reactive gas of water and reduce film performance, solve the splitting produced in construction process, the disadvantages such as foaming; Solve two-component polyurethane adhesive and stick the impact that agent VOC content is high, component property is unstable, adhesive property is subject to extraneous hydroxyl material; As the macromolecule filming thing of sizing agent, greatly reduce the VOC discharge capacity of sizing agent and enhance sizing agent stability, glue-line bubble disadvantage will solve at all, effectively inhibit the defect of material itself to occur, difficulty of construction is reduced, also reduces the cost of adhesive for polyurethane simultaneously.
Embodiment
The preparation of acrylic acid modified resin
Embodiment 1
The synthesis of table 1 polyester portion selects polyprotonic acid and polyvalent alcohol to feed intake table
Table 2. acrylic resin polymer monomers initiator feeds intake table
A. to the monomer added with stirring, in the four-hole bottle of thermometer and rectifying column in table 1 except cocinic acid, control still temperature and be no more than 230 DEG C, column temperature 95-100 DEG C, the water yield is weighed up after reaction 2-4hr, survey acid number and be less than 5mgKOH/g, add cocinic acid, continue reaction 1-1.5hr survey acid number and be less than 5mgKOH/g, be cooled to 100 DEG C.
B. add 150g propylene glycol monomethyl ether and 80g ethylene glycol monobutyl ether, control temperature is to 90-100 DEG C;
C. at 90-100 DEG C, by methyl methacrylate (MMA), butyl acrylate (BA), lauryl methacrylate(LMA) (LMA), glycidyl methacrylate (GMA), the monomers such as isobornyl methacrylate (IBOMA) and Diisopropyl azodicarboxylate (AIBN) mix, be added drop-wise in four-hole bottle, time for adding is 2 ~ 2.5hr, after dropwising, add 3gAIBN, insulation 3hr;
C. after being incubated 3hr, being cooled to 50 DEG C, adding 41g triethylene tetramine, insulation 2hr;
D. add the neutralization of 52g formic acid, namely obtain the acrylic acid modified resin of aqueous double-component polyurethane sizing agent.
Embodiment 2
The synthesis of table 3 polyester portion selects polyprotonic acid and polyvalent alcohol to feed intake table
Table 4. acrylic resin polymer monomers initiator feeds intake table
A. to the monomer added with stirring, in the four-hole bottle of thermometer and rectifying column in table 1 except behenic acid, control still temperature and be no more than 230 DEG C, column temperature 95-100 DEG C, the water yield is weighed up after reaction 2-4hr, survey acid number and be less than 5mgKOH/g, add behenic acid, continue reaction 1-1.5hr survey acid number and be less than 5mgKOH/g, be cooled to 100 DEG C.
B. at 100 DEG C, by methyl methacrylate (MMA), butyl acrylate (BA), butyl methacrylate (BMA), glycidyl methacrylate (GMA), the monomers such as isobornyl methacrylate (IBOMA) and benzoyl peroxide (BPO) mix, be added drop-wise in four-hole bottle, time for adding asks 2 ~ 2.5hr, after dropwising, add 3gBPO, insulation 3hr;
C. after being incubated 3hr, being cooled to 50 DEG C, adding 122g diethanolamine, insulation 2hr;
D. add the neutralization of 65g acetic acid, namely obtain the acrylic acid modified resin of aqueous double-component polyurethane sizing agent.
Embodiment 3
The synthesis of table 5 polyester portion selects polyprotonic acid and polyvalent alcohol to feed intake table
Table 6. acrylic resin polymer monomers initiator feeds intake table
A. to the monomer added with stirring, in the four-hole bottle of thermometer and rectifying column in table 1 except behenic acid, control still temperature and be no more than 230 DEG C, column temperature 95-100 DEG C, the water yield is weighed up after reaction 2-4hr, survey acid number and be less than 5mgKOH/g, add behenic acid, continue reaction 1-1.5hr survey acid number and be less than 5mgKOH/g, be cooled to 110 DEG C.
B. at 110 DEG C, by methyl methacrylate (MMA), butyl acrylate (BA), lauryl methacrylate(LMA) (LMA), glycidyl methacrylate (GMA), the monomers such as isobornyl methacrylate (IBOMA) and peroxidized t-butyl perbenzoate (TBPB) mix, be added drop-wise in there-necked flask, time for adding asks 2 ~ 2.5hr, after dropwising, add 3gTBPB, insulation 3hr;
C. after being incubated 3hr, being cooled to 50 DEG C, adding 54g diethanolamine and 9.3g AMP-95 (2-amino-2-methyl-1-propanol), insulation 2hr;
D. add 78.6g lactic acid neutralization, namely obtain the acrylic acid modified resin of aqueous double-component polyurethane sizing agent material.
Embodiment 4
Table 7. acrylic resin polymer monomers initiator feeds intake table
A. in the there-necked flask with stirring and thermometer, add propylene glycol monomethyl ether 650g and butyl glycol ether 150g, be warming up to 120 DEG C;
B. at 120 DEG C, methyl methacrylate (MMA), butyl acrylate (BA), lauryl methacrylate(LMA) (LMA), glycidyl methacrylate (GMA), the monomers such as isobornyl methacrylate (IBOMA) and peroxidized t-butyl perbenzoate (TBPB) mix, be added drop-wise in there-necked flask, time for adding asks 2-2.5hr, after dropwising, add 3gTBPB, insulation 3hr;
C. after being incubated 3hr, being cooled to 50 DEG C, adding 75g monomethyl-ethanolamine, insulation 2hr;
D. add the neutralization of 46g formic acid, namely obtain the acrylic acid modified resin of aqueous double-component polyurethane sizing agent.
Embodiment 5
Table 8. acrylic resin polymer monomers initiator feeds intake table
A. in the there-necked flask with stirring and thermometer, add propylene glycol monomethyl ether, be warming up to 90 DEG C;
B. at 90 DEG C, by (methyl) alkyl acrylate, vinylbenzene (St), butyl acrylate (BA), lauryl methacrylate(LMA) (LMA), glycidyl methacrylate (GMA), the monomers such as isobornyl methacrylate (IBOMA) and peroxidized t-butyl perbenzoate (TBPB) mix, be added drop-wise in there-necked flask, time for adding asks 2 ~ 2.5hr, when dropwising rear insulation 3hr;
C. after being incubated 3hr, being cooled to 50 DEG C, adding 23g monomethyl-ethanolamine, insulation 2hr;
D. add the neutralization of 14g formic acid, namely obtain the acrylic acid modified resin of aqueous double-component polyurethane sizing agent.
Resin after neutralization can be scattered in water easily.
Aqueous double-component polyurethane sizing agent is prepared
Carry out being obtained by reacting the larger resin Composition of molecular weight as component A using acrylic acid modified resin or according to the ratio of 1:0.9-0.99 and polyisocynate monomer; Use the thinner such as 1-Methoxy-2-propyl acetate or N-Methyl pyrrolidone will be diluted to concentration for 60%-80%, as B component containing polyisocyanate species solidifying agent.
By A, B two component of 100:5-50, mixing and stirring, the 10-120 that adds water again in upper step ratio is adjusted to appropriate viscosity and glueds joint.This sizing agent working life is 3-6hr, and viscosity slightly rises afterwards.Moisture after gluing in warm air drying removing glue and organic solvent, then glued joint, and is placed on 40-60 DEG C of solidification 50hr, also can heats up and carry out fast setting as 90 DEG C of 20min, namely reach good Joint strength after solidification.
Claims (10)
1. novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin, comprises the following steps:
(1) interpolation or synthetic macromolecule resin 0-80 weight part, add in reactor by polyprotonic acid and polyvalent alcohol, heats up, still temperature 160-240 DEG C, column temperature 90-100 DEG C, and reaction water outlet, measures the water yield, controls acid number and be less than 5mgKOH/g;
(2) by the solvent of 0 ~ 60 weight part, add in there-necked flask, be warming up to 60 DEG C-150 DEG C;
(3) drip the mixture of 10-90 part vinyl or acrylicacidandesters class and initiator under stirring state at 60 ~ 150 DEG C, 2-6hr dropwises, and dropwises rear 60-150 DEG C of insulation 2-4hr.
(4) be cooled to 50 ~ 90 DEG C, add 0.1-20 part organic amine, under the state stirred, insulation 0.5-3hr;
(5) insulation adds 0-20 part acid, stirs 0.5-2hr and namely obtains the acrylic acid modified resin of aqueous double-component polyurethane sizing agent.
2. one of as claimed in claim 1 novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin, it is characterized in that: the resin that (5) are obtained gets 0.9-0.99 according to the amount of substance of isocyanic ester/hydroxyl, and add the glycerol/ethylene glycol of 0-0.15, add TDI, MDI, HDI or PAPI isocyanic ester at 80-105 DEG C, carry out backflow chain extending reaction 3-5hr, obtain the acrylic acid modified resin of adhesive for polyurethane.
3. one of as claimed in claim 1 novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin, it is characterized in that: formula adopts 0-50 part macromolecule resin, 10-60 part solvent, 20-80 part vinyl or acrylicacidandesters class monomer, 0.1-8 part initiator, 0.1-10 part organic amine, 0.1-10 part acid.
4. a kind of novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin as claimed in claim 1, it is characterized in that: described macromolecule resin is selected from vibrin, epoxy resin, Synolac, one or more in resol.
5. a kind of novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin as claimed in claim 1, it is characterized in that: macromolecule resin is selected from polyester or Synolac, the monomer selected in its building-up process comprises: hexanodioic acid, MALEIC ANHYDRIDE, terephthalic acid, m-phthalic acid, trimellitic acid 1,2-anhydride, one or more in TriMethylolPropane(TMP), neopentyl glycol, dimethylol propionic acid, ricinolic acid, behenic acid, cocinic acid, synthetic fatty acid.
6. a kind of novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin as claimed in claim 1, it is characterized in that: described solvent is selected from ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, butanols, alcohol ester 12, N-Methyl pyrrolidone, one or more in butyl.
7. a kind of novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin as claimed in claim 1, it is characterized in that: described vinyl or acrylicacidandesters class monomer are selected from one or more in vinylbenzene, vinylformic acid, methacrylic acid, butyl methacrylate, methyl methacrylate, butyl acrylate, (methyl) glycidyl acrylate, 1,2-epoxy-4-vinyl cyclohexane, lauryl methacrylate(LMA), isobornyl methacrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate.
8. a kind of novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin as claimed in claim 1, it is characterized in that: described initiator is selected from dibenzoyl peroxide, peroxidized t-butyl perbenzoate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), cyclohexanone peroxide, tertbutyl peroxide, dicumyl peroxide, hydrogen peroxide, persulphate, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride, 2, 2 '-azo two (2-methyl-4-carboxyl butyronitrile), 2, one or more in 2 '-azo two (2-cyanogen propane-1-sulfonate).
9. a kind of novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin as claimed in claim 1, it is characterized in that: described organic amine is selected from one or more in diethylenetriamine, triethylene tetramine, monomethyl-ethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol.
10. a kind of novel aqueous two-component polyurethane adhesive sticks the preparation method of agent with acrylic acid modified resin as claimed in claim 1, it is characterized in that: described acid is selected from one or more in hydrochloric acid, sulfuric acid, phosphoric acid, tetra-sodium, polyphosphoric acid, citric acid, formic acid, acetic acid, lactic acid.
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| CN105348487A (en) * | 2015-12-16 | 2016-02-24 | 江南大学 | Preparation method of ricinolic acid based UV cured water-base resin |
| CN109081902A (en) * | 2017-06-14 | 2018-12-25 | 万华化学集团股份有限公司 | A kind of adhesive of artificial board of no aldehyde addition and with its manufacture without aldehyde addition wood-based plate |
| CN111454423A (en) * | 2020-04-29 | 2020-07-28 | 东莞市冠力胶业有限公司 | Water-based vacuum plastic and preparation method thereof |
| CN112625637A (en) * | 2020-12-10 | 2021-04-09 | 福建国邦新材料有限公司 | Single-component solvent-free polyurethane adhesive and preparation method thereof |
| CN114989436A (en) * | 2022-05-30 | 2022-09-02 | 浙江鹏孚隆新材料有限公司 | Water-based polyester modified organic silicon resin, preparation method and application thereof |
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Cited By (9)
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| CN105348487A (en) * | 2015-12-16 | 2016-02-24 | 江南大学 | Preparation method of ricinolic acid based UV cured water-base resin |
| CN105348487B (en) * | 2015-12-16 | 2018-03-20 | 江南大学 | A kind of preparation method of castor oil acidic group UV curable water-borne resins |
| CN109081902A (en) * | 2017-06-14 | 2018-12-25 | 万华化学集团股份有限公司 | A kind of adhesive of artificial board of no aldehyde addition and with its manufacture without aldehyde addition wood-based plate |
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| CN112625637A (en) * | 2020-12-10 | 2021-04-09 | 福建国邦新材料有限公司 | Single-component solvent-free polyurethane adhesive and preparation method thereof |
| CN114989436A (en) * | 2022-05-30 | 2022-09-02 | 浙江鹏孚隆新材料有限公司 | Water-based polyester modified organic silicon resin, preparation method and application thereof |
| CN114989436B (en) * | 2022-05-30 | 2023-04-28 | 浙江鹏孚隆新材料有限公司 | Water-based polyester modified organic silicon resin, preparation method and application thereof |
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