CN100340598C - Water dispersible end capping diisocyanate cross-linking agent and its preparation method - Google Patents
Water dispersible end capping diisocyanate cross-linking agent and its preparation method Download PDFInfo
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- CN100340598C CN100340598C CNB2006100351982A CN200610035198A CN100340598C CN 100340598 C CN100340598 C CN 100340598C CN B2006100351982 A CNB2006100351982 A CN B2006100351982A CN 200610035198 A CN200610035198 A CN 200610035198A CN 100340598 C CN100340598 C CN 100340598C
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Abstract
The present invention relates to a water-dispersible blocked diisocyanate crosslinking agent and a preparing method thereof, which is characterized in that the crosslinking agent is obtained by the addition reaction of 100 parts by weight of diisocyanate, 2.9 to 28 parts of polyatomic alcohol, 7.8 to 45 parts of compounds disclosed in the formula (1) and 100 to 160 parts of blocking agents under the action of solvent, or under the action of solvent and catalysts. The crosslinking agent of the present invention can be blended with water at optional ratios, and can be stored for more than one year at room temperature; in addition, the crosslinking agent can effectively increase the mechanical property of emulsion. Thus, the crosslinking agent is suitable for polyaminoester or water-dispersible solution of polymers prepared by free radical polymerization. Especially, the crosslinking agent is used for water-dispersible coating and bonding agents. In the formula (1), R represents H, a hydroxymethyl group or an alkyl group containing 1 to 10 carbon atoms.
Description
Technical field
The present invention relates to a kind of linking agent, relate to a kind of water dispersible end capping diisocyanate cross-linking agent specifically, also relate to the preparation method of this linking agent in addition.
Background technology
Along with the establishment of various countries' environmental regulation and the raising day by day of environmental consciousness, particularly European solvent management rules in 1994 are announced the quantity discharged of organic solvent are had higher requirement, and make water-borne coatings and aqueous adhesive become the focus of research gradually.But present most of water-borne coatings and aqueous adhesive is water-soluble relatively poor, and its over-all properties especially solvent resistance compare with solvent-based adhesive with solvent based coating with water tolerance and still have a certain distance.Therefore how improving the performance of water-borne coatings and aqueous adhesive, make it can replace solvents type coating and solvent-based adhesive, be the problem that research and development person extremely pays close attention to.
Improving cross-linking properties is the importance that improves water-borne coatings and aqueous adhesive performance.General crosslinked means mainly contain two kinds: interior crosslinked and external crosslinking.In crosslinked be that selection by raw material makes lightly crosslinked emulsion, external crosslinking is to add linking agent before use in emulsion, is equivalent to bicomponent system.The interior crosslinked restriction that still has degree of crosslinking, therefore by contrast, the emulsion property that external crosslinking makes is better, and can regulate the performance of filming by changing the consumption of linking agent.But still there is the problem that working life is short and need prepare before use in the employed linking agent of external crosslinking method at present.
Summary of the invention
The objective of the invention is to develop a kind of stability in storage and linking agent easy to use.
The present invention passes through vulcabond, polyvalent alcohol, 2,2-dihydroxymethyl alkanoic acid and end-capping reagent react under the effect of solvent and catalyzer, in the linking agent that obtains-the NCO group seals by end-capping reagent fully, therefore have stability in storage preferably, also have good water dispersible, can directly add in coating and the tackiness agent in addition, obtain well behaved water-borne coatings and aqueous adhesive, thereby realized purpose of the present invention.
Water dispersible end capping diisocyanate cross-linking agent of the present invention, it is characterized in that forming by addition reaction and obtain: by the mole umber by following raw material, 100 parts of vulcabond, 2.9～28 parts of polyvalent alcohols, 7.8～45 parts of the compounds of formula (1), 100～160 parts of end-capping reagents, the R in the formula (1) are represented H, methylol or are contained the alkyl of 1～10 carbon atom.
Formula (1)
Described vulcabond can be one or more the mixture in aliphatic diisocyanate or the aromatic diisocyanate, described aliphatic diisocyanate can be a tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene diisocyanates, the decamethylene vulcabond, ten dimethylene diisocyanates, ten tetramethylene diisocyanate, trimethyl cyclohexane vulcabond or tetramethyl-hexane diisocyanate etc., can be 1,4-vulcabond hexanaphthene, 1,3-vulcabond hexanaphthene, 1,2-vulcabond hexanaphthene, isophorone diisocyanate, 2,4-two isocyanatos-1-methylcyclohexane or 2,6-two isocyanatos-1-methylcyclohexane etc., described aromatic diisocyanate can be 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, the inferior Xylene Diisocyanate of tetramethyl-, the methylene phenylene diisocyanate, 2,4-vulcabond ditan or 4,4 '-vulcabond ditan, benzene 1,3-vulcabond or benzene 1, the 4-vulcabond, 1-chlorine phenylene 2, the 4-vulcabond, phenylene 1, the 5-vulcabond, the biphenylene vulcabond, 4,4 '-two isocyanatos-3,3 '-dimethyl diphenyl, 3-MDPM 4,4 '-vulcabond or 4,4 '-vulcabond phenyl ether etc., preferably 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 2,4-vulcabond ditan, 4,4 '-vulcabond ditan or isophorone diisocyanate etc.
Described polyvalent alcohol can be trivalent alcohol, tetravalent alcohol or pentavalent alcohol, as TriMethylolPropane(TMP), trimethylolethane, glycerine, 1,2,6-hexanetriol, tris(2-hydroxy ethyl)isocyanurate, trolamine, tri-isopropanolamine, tetramethylolmethane or Xylitol etc., preferably TriMethylolPropane(TMP), trimethylolethane or glycerine.
Described end-capping reagent can be one or more the mixture in methyl ethyl ketoxime, acetoxime, hexanolactam, phenol or the phenol substituent, and described phenol substituent can be nitrophenols, chlorophenol or alkyl substituted phenol etc.
The preparation method of water dispersible end capping diisocyanate cross-linking agent of the present invention is characterized in that comprising the steps:
Vulcabond, the compound of polyvalent alcohol and formula (1), under the effect of solvent, or under the acting in conjunction of solvent and catalyzer, in 60～90 ℃ of reactions, when reach-during the calculated value of NCO group content, add end-capping reagent, continue reaction at 80～110 ℃, do not have appearance-NCO group at 2250～2270cm up to infrared detection
-1The place charateristic avsorption band the time stopped reaction, in and carboxylic group, obtain product.
Described catalyzer can be a preparation urethane catalyzer commonly used, dibutyl tin laurate for example, consumption is a vulcabond, the 0%-0.1% of the compound total mass of polyvalent alcohol and formula (1), described solvent can be hydrophilic solvent such as acetone, N-Methyl pyrrolidone etc., or hydrophobic nature solvent such as toluene etc., preferably N-Methyl pyrrolidone, in and carboxylic group can adopt triethylamine, dimethylethanolamine, methyl diisopropylamine or ammonia etc., preferably adopt triethylamine.
The quality of carboxylic group accounts for 1%～5.1% of linking agent in the water dispersible end capping diisocyanate cross-linking agent of the present invention.This linking agent can with water with the arbitrary proportion blend, and at room temperature can store above 1 year, can make the degree of crosslinking of system have certain controllability, and improve the mechanical property of emulsion effectively, but the linking agent of the water dispersion soln of the polymkeric substance that therefore is applicable to urethane or makes by radical polymerization, but especially for the linking agent of water dispersion paints and tackiness agent.
Embodiment
Embodiment 1:
With 17.41g 2,4 toluene diisocyanate (0.1mol), 3.76g TriMethylolPropane(TMP) (0.028mol) and 1.05g dimethylol propionic acid (compound of formula (1), wherein R=CH
3, 0.0078mol) and the 8g N-Methyl pyrrolidone, under 60 ℃ and condition of stirring, react 3 hours, extremely-NCO content reaches 13.8%.Under the situation of logical nitrogen, be warming up to 80 ℃, add 8.7g methyl ethyl ketoxime (0.1mol), react 2 hours extremely-NCO is fully by end-blocking.Through infrared detection, there is not appearance-NCO group at 2250～2270cm
-1The charateristic avsorption band at place.Be cooled to 50 ℃, adding 0.79g (0.0078mol) triethylamine neutralizes, and reacts to add entry 23.7g dispersion after about 10 minutes, but obtains the agent of flaxen stabilized uniform end-sealed type water decentralized crosslinking.Its carboxylic group quality accounts for 1.1% (calculated value) of linking agent total mass, solid content 50% (calculated value), pH8.2, viscosity 887mPas.
Embodiment 2:
With the compound dimethylolpropionic acid of 44.46g isophorone diisocyanate (0.2mol), 2.06g glycerine (0.022mol) and 2.37g formula (1) (R=C wherein
2H
5) (0.016mol) and the 8gN-methyl-2-pyrrolidone, the 0.04g dibutyl tin laurate at 80 ℃ down and under the condition of stirring, reacted 3 hours, extremely-NCO content reaches 22.3%.Under the situation of logical nitrogen, add 8.7g (0.1mol) methyl ethyl ketoxime and 11.3g hexanolactam (0.1mol), react 2 hours extremely-NCO is fully by end-blocking.Through infrared detection, there is not appearance-NCO group at 2250～2270cm
-1The charateristic avsorption band at place.Be cooled to 50 ℃, adding 1.6g (0.016mol) triethylamine neutralizes, and reacts to add entry 62.5g dispersion after about ten minutes, but obtains the agent of flaxen stabilized uniform end-sealed type water decentralized crosslinking.Its carboxylic group quality accounts for 1.02% (calculated value) of linking agent total mass, solid content 50% (calculated value), pH8.3, viscosity 875mPas.
Embodiment 3:
With 17.41g 2, the compound (wherein R=H) of 6-tolylene diisocyanate (0.1mol), 0.46g TriMethylolPropane(TMP) (0.0034mol) and 5.49g formula (1) (0.045mol) and the 10g N-Methyl pyrrolidone, under 60 ℃ and condition of stirring, reacted 3 hours, and reached 12.5% to-NCO content.Under the situation of logical nitrogen, be warming up to 80 ℃, add 11.3g hexanolactam (0.1mol), react 3 hours extremely-NCO is fully by end-blocking.Through infrared detection, there be not the charateristic avsorption band of appearance-NCO group at 2250～2270cmu place.Be cooled to 50 ℃, adding triethylamine 4.5g (0.045mol) neutralizes, and reacts to add entry 29.2g dispersion after about ten minutes, but obtains the agent of flaxen stabilized uniform end-sealed type water decentralized crosslinking.Its carboxylic group quality accounts for 5.17% (calculated value) of linking agent total mass, solid content 50% (calculated value), pH8.4, viscosity 925mPas.
Embodiment 4:
With 22.23g isophorone diisocyanate (0.1mol), 8.7g 2, the compound of 6-tolylene diisocyanate (0.05mol), 0.41g glycerine (0.0044mol) and 5.8g formula (1) (R=CH wherein
3) (0.043mol) and the 0.03g dibutyl tin laurate, 10g toluene at 90 ℃ down and under the condition of stirring, reacted 3 hours, extremely-NCO content reaches 17.7%.Under the situation of logical nitrogen, add 27g hexanolactam (0.24mol), react 3 hours extremely-NCO is fully by end-blocking.Through infrared detection, there is not appearance-NCO group at 2250～2270cm
-1The charateristic avsorption band at place.Be cooled to 50 ℃, adding 4.3g triethylamine (0.043mol) neutralizes, and reacts to add entry 58.5g dispersion after about ten minutes, but obtains the agent of flaxen stabilized uniform end-sealed type water decentralized crosslinking.Its carboxylic group quality accounts for 2.83% (calculated value) of linking agent total mass, solid content 50% (calculated value), pH8.4, viscosity 900mPas.
Embodiment 5:
With the compound of 26.12g 2,4 toluene diisocyanate (0.15mol), 1g glycerine (0.011mol) and 8.84g formula (1) (R=C wherein
10H
21) (0.034mol) and the 10g N-Methyl pyrrolidone, at 60 ℃ down and under the condition of stirring, reacted 3 hours, extremely-NCO content reaches 18.1%.Under the situation of logical nitrogen, be warming up to 110 ℃, add 20.7g phenol (0.22mol), react 5 hours, be cooled to 50 ℃ of reactions 5 hours extremely-NCO is fully by end-blocking.Through infrared detection, there is not appearance-NCO group at 2250～2270cm
-1The charateristic avsorption band at place.Adding 3.3g triethylamine (0.033mol) neutralizes, and reacts to add entry 50g dispersion after about ten minutes, but obtains the agent of flaxen stabilized uniform end-sealed type water decentralized crosslinking.Its carboxylic group quality accounts for 2.55% (calculated value) of linking agent total mass, solid content 50% (calculated value), pH8.4, viscosity 900mPas.
Embodiment 6:
With the compound of 16.82g hexamethylene diisocyanate (0.1mol), 3.4g tetramethylolmethane (0.021mol) and 1.1g formula (1) (R=CH wherein
3) (0.0082mol) and the 0.03g dibutyl tin laurate, the 10g N-Methyl pyrrolidone at 80 ℃ down and under the condition of stirring, reacted 3 hours, extremely-NCO content reaches 13.4%.Under the situation of logical nitrogen, add 9.57g methyl ethyl ketoxime (0.11mol), react 2 hours extremely-NCO is fully by end-blocking.Through infrared detection, there is not appearance-NCO group at 2250～2270cm
-1The charateristic avsorption band at place.Be cooled to 50 ℃, adding 0.83g triethylamine (0.0082mol) neutralizes, and reacts to add entry 21.7g dispersion after about ten minutes, but obtains the agent of flaxen stabilized uniform end-sealed type water decentralized crosslinking.Its carboxylic group quality accounts for 1.15% (calculated value) of linking agent total mass, solid content 50% (calculated value), pH8.4, viscosity 900mPas.
Embodiment 7:
With the compound of 26.12g 2,4 toluene diisocyanate (0.15mol), 1g glycerine (0.011mol) and 4.55g formula (1) (R=CH wherein
3) (0.034mol) and the 10g N-Methyl pyrrolidone, at 60 ℃ down and under the condition of stirring, reacted 3 hours, extremely-NCO content reaches 20.1%.Under the situation of logical nitrogen, be warming up to 100 ℃, add 28.27g para-chlorophenol (0.22mol), react 5 hours, be cooled to 50 ℃ of reactions 5 hours extremely-NCO is fully by end-blocking.Through infrared detection, there is not appearance-NCO group at 2250～2270cm
-1The charateristic avsorption band at place.Adding 3.3g triethylamine (0.033mol) neutralizes, and reacts to add entry 53.2g dispersion after about ten minutes, but obtains the agent of flaxen stabilized uniform end-sealed type water decentralized crosslinking.Its carboxylic group quality accounts for 2.41% (calculated value) of linking agent total mass, solid content 50% (calculated value), pH8.4, viscosity 900mPas.
Embodiment 8:
Polyurethane-acrylate (PUA) composite emulsion of self-control hydroxyl, hydroxyl value is 72.4mgKOH/g, and solid content is 33%, and the pH value is 7.5.
But with the end-sealed type water dispersible polyisocyanate linking agent of the embodiment of the invention 1, join from making in the PUA composite emulsion, blend under mechanical stirring makes the emulsion of stable uniform.The quality of linking agent accounts for 6% of system.
Elder generation at 50 ℃ of following drying and forming-films, again with prepared film, is placed to this emulsion 130 ℃ and toasts half an hour down.Comparative film is changes of mechanical properties before and after high bake.The results are shown in Table 1.
Table 1 contains film changes of mechanical properties before and after 130 ℃ of high bakes of linking agent of the present invention
| Mechanical property | Before the baking | After the baking |
| Tensile strength (MPa) elongation at break (%) | 11.40 34.84 | 278.90 117.04 |
Claims (8)
1. water dispersible end capping diisocyanate cross-linking agent, it is characterized in that forming and obtaining by following preparation method by following raw material, described raw material is formed by the mole umber, be 100 parts of vulcabond, 2.9～28 parts of polyvalent alcohols, 7.8～45 parts of the compounds of formula (1), 100～160 parts of end-capping reagents, described preparation method comprises the steps: vulcabond, the compound of polyvalent alcohol and formula (1), under the effect of solvent, or under the acting in conjunction of solvent and catalyzer, in 60～90 ℃ of reactions, when reach-during the calculated value of NCO group content, add end-capping reagent, continue reaction, do not have appearance-NCO group at 2250～2270cm up to infrared detection at 80～110 ℃
-1The place charateristic avsorption band the time stopped reaction, in and carboxylic group,
Formula (1)
R in its Chinese style (1) represents H, methylol or contains the alkyl of 1～10 carbon atom.
2. according to a kind of water dispersible end capping diisocyanate cross-linking agent of claim 1, it is characterized in that described vulcabond is one or more the mixture in aliphatic diisocyanate or the aromatic diisocyanate, described polyvalent alcohol is trivalent alcohol, tetravalent alcohol or pentavalent alcohol, and described end-capping reagent is one or more the mixture in methyl ethyl ketoxime, acetoxime, hexanolactam, phenol or the phenol substituent.
3. according to a kind of water dispersible end capping diisocyanate cross-linking agent of claim 2, it is characterized in that described aliphatic diisocyanate is a tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene diisocyanates, the decamethylene vulcabond, ten dimethylene diisocyanates, ten tetramethylene diisocyanate, trimethyl cyclohexane vulcabond or tetramethyl-hexane diisocyanate, 1,4-vulcabond hexanaphthene, 1,3-vulcabond hexanaphthene, 1,2-vulcabond hexanaphthene, isophorone diisocyanate, 2,4-two isocyanatos-1-methylcyclohexane or 2,6-two isocyanatos-1-methylcyclohexane, described aromatic diisocyanate is 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, the inferior Xylene Diisocyanate of tetramethyl-, the methylene phenylene diisocyanate, 2,4-vulcabond ditan, 4,4 '-vulcabond ditan, benzene 1,3-vulcabond or benzene 1, the 4-vulcabond, 1-chlorine phenylene 2, the 4-vulcabond, phenylene 1, the 5-vulcabond, the biphenylene vulcabond, 4,4 '-two isocyanatos-3,3 '-dimethyl diphenyl, 3-MDPM 4,4 '-vulcabond or 4,4 '-vulcabond phenyl ether etc., described polyvalent alcohol is a TriMethylolPropane(TMP), trimethylolethane, glycerine, 1,2, the 6-hexanetriol, tris(2-hydroxy ethyl)isocyanurate, trolamine, tri-isopropanolamine, tetramethylolmethane or Xylitol, described phenol substituent is a nitrophenols, chlorophenol or alkyl substituted phenol.
4. according to a kind of water dispersible end capping diisocyanate cross-linking agent of claim 1 or 2, it is characterized in that described vulcabond is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-vulcabond ditan, 4,4 '-vulcabond ditan or isophorone diisocyanate, described polyvalent alcohol are TriMethylolPropane(TMP), trimethylolethane or glycerine.
5. the preparation method of a water dispersible end capping diisocyanate cross-linking agent is characterized in that comprising the steps:
Vulcabond 100 mass parts, compound 7.8～45 mass parts of polyvalent alcohol 2.9～28 mass parts and formula (1), under the effect of solvent, or under the acting in conjunction of solvent and catalyzer, in 60～90 ℃ of reactions, when reach-during the calculated value of NCO group content, add 100～160 mass parts end-capping reagents, continue reaction at 80～110 ℃, do not have appearance-NCO group at 2250～2270cm up to infrared detection
-1The place charateristic avsorption band the time stopped reaction, in and carboxylic group, obtain product,
Formula (1)
R in its Chinese style (1) represents H, methylol or contains the alkyl of 1～10 carbon atom.
6. according to the preparation method of a kind of water dispersible end capping diisocyanate cross-linking agent of claim 5, it is characterized in that described catalyzer is a dibutyl tin laurate, consumption is a vulcabond, the 0%-0.1% of the compound total mass of polyvalent alcohol and formula (1), described solvent is hydrophilic solvent or hydrophobic nature solvent, adopts in triethylamine, dimethylethanolamine, methyl diisopropylamine or the ammonia and carboxylic group.
7. according to the preparation method of a kind of water dispersible end capping diisocyanate cross-linking agent of claim 6, it is characterized in that described hydrophilic solvent is acetone, N-Methyl pyrrolidone, described hydrophobic nature solvent is a toluene, adopts in the triethylamine and carboxylic group.
8. according to the preparation method of a kind of water dispersible end capping diisocyanate cross-linking agent of claim 6, it is characterized in that described hydrophilic solvent is a N-Methyl pyrrolidone.
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| CN101503610B (en) * | 2008-02-04 | 2013-04-03 | 上海巨安科技有限公司 | Enclosed type self-crosslinking single component polyurethane binder and preparation thereof |
| DE102009003512A1 (en) * | 2009-02-20 | 2010-09-02 | Elantas Gmbh | Environmentally friendly solderable wire enamel |
| CN101638471B (en) * | 2009-09-01 | 2011-06-29 | 陕西科技大学 | Method for preparing water-base cation blocked polyisocyanates crosslinking and curing agent |
| CN102443135B (en) * | 2011-10-31 | 2014-05-07 | 西安邮电学院 | Single-component curing agent capable of being deblocked at low temperature |
| CN103353489B (en) * | 2013-06-24 | 2015-02-04 | 黄河三角洲京博化工研究院有限公司 | Detection method for detecting isophorone diisocyanate by using gas chromatography-mass spectrometer |
| CN108219340A (en) * | 2018-01-03 | 2018-06-29 | 温州市登达化工有限公司 | A kind of soft cross-linked polyurethane materials and preparation method thereof |
| CN111777732A (en) * | 2020-07-24 | 2020-10-16 | 广东德美精细化工集团股份有限公司 | Solvent-free blocked polyurethane cross-linking agent and preparation method thereof |
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| US5115071A (en) * | 1991-04-09 | 1992-05-19 | Air Products And Chemicals, Inc. | High performance polyurethane coating compositions and processes for making same |
| CN1424345A (en) * | 2002-12-20 | 2003-06-18 | 深圳市飞扬实业有限公司 | Preparation of polyurethane curing agent with low free toluene diisocyanate |
| CN1116328C (en) * | 2000-12-05 | 2003-07-30 | 上海市涂料研究所 | Paint curing agent 4,2'-and 4,4'-diphenyl methane diisocyanate prepolymer and its prepn |
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| US5115071A (en) * | 1991-04-09 | 1992-05-19 | Air Products And Chemicals, Inc. | High performance polyurethane coating compositions and processes for making same |
| CN1116328C (en) * | 2000-12-05 | 2003-07-30 | 上海市涂料研究所 | Paint curing agent 4,2'-and 4,4'-diphenyl methane diisocyanate prepolymer and its prepn |
| CN1424345A (en) * | 2002-12-20 | 2003-06-18 | 深圳市飞扬实业有限公司 | Preparation of polyurethane curing agent with low free toluene diisocyanate |
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