CN1076712A - Single component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof - Google Patents
Single component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof Download PDFInfo
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- CN1076712A CN1076712A CN 93103057 CN93103057A CN1076712A CN 1076712 A CN1076712 A CN 1076712A CN 93103057 CN93103057 CN 93103057 CN 93103057 A CN93103057 A CN 93103057A CN 1076712 A CN1076712 A CN 1076712A
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Abstract
The present invention relates to a kind of single component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof.It contains polynary Aethoxy Sklerol and/or Viscotrol C, polyesterols resin, organic multiple isocyanate, catalyzer, solvent and its properties-correcting agent.The glue of filming of the present invention has superior moisture-resistant curing, water-tight corrosion-proof, ageing resistance, anti-basic crack and retractility, and weathering resistance is mainly used in waterproof construction, industrial equipment anticorrosion, also as bonding and sealing agent etc.The detailed manufacturing processed of this glue of filming is disclosed.The most outstanding characteristics of filming of the present invention are to meet moisture-curable and do not produce the reaction bubble, thereby have avoided polyurethane water-proof glue to meet the common fault that moisture promptly produces " honeycomb " shape bubble.
Description
The present invention relates to a kind of single-component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof, in more detail, it be with polyisocyanates, Viscotrol C, polyesterols and or polynary Aethoxy Sklerol be main raw material, be prepared into a kind of monocomponent polyurethane waterproof coating glue, to be liquid state in pail pack absorb the moisture content in air and the basic unit voluntarily after coating and be solidified into and be rich in the waterproof membrane that elasticity does not produce pore for it.Easy construction has good weathering resistance, oil-resisting and heat-resisting wear resistance, and has the ageing-resistant performance of ultraviolet light and ozone.Solvability and aerial volatility are almost nil and improved its health level use range greatly in water because age-inhibiting addition has entered crosslink polymer network.It can be widely used in building roof, ground, the waterproofing work of vault and seam, hardware anticorrosion, the bonding and floor, kindergarten of woodwork floor family property, mosaic, athletic ground etc.
Topic of the present invention is stated and is filmed that to have a curing speed moderate, and moisture resistance is extremely strong during construction, does not produce bubble after the film forming, uses more conveniently, is its outstanding advantage.
At present, be applied to be that urethane series is the outstanding person of suitableeer national conditions, but all be two dried curing urethane coating of component in the high-grade water-proof material of building such as prefabricated component roofing, vault, pond and body of wall of concrete or gas concrete.Yet, the usefulness wet-cured type that relatively suits in most of working-yards and the environment.Though the dried curable polyurethane performance of two components is fabulous, two kinds of components need the interim allotment in working-yard that inconvenience is arranged first, and allocate and inhomogeneously then can cause degradation, even aging speed is accelerated; Second need butt to solidify, thereby limited their range of application and their sale time and market.
Since the eighties, the consumption of external single-component constantly increases.In Japan, the consumption of single-component and two components reaches fair, and the technology status of single-component or moisture curing is at the clear 62-2232258 of Japanese Patent, clear 62-57412, and clear 62-153340 embodies in the documents such as clear 62-236812 to some extent; DE-3629237A1 has embodied the coating material solidified invention of organic silicon polyurethane; But these invent raw materials used costing an arm and a leg, the national conditions of difficult moderate state building.In the U.S., estimate that the consumption of the nineties single-component has surpassed the consumption of two components.At home, a spot of trial product also appearred in the history of existing more than ten years of the research of mono component wet solidifying sealing agent on the market, but from the problem that performance is packed and used several respects to exist, did not have breakthrough so far.Except single-component (film) paint, do not retrieve single-component (resisting) moisture cure urethanes waterproof glue or close patent of invention document.
Purpose of the present invention is the thick film waterproof coating glue that a kind of single-component (resisting) moisture curing, reactionless bubble will be provided, and it has following good performance:
A. very high tensile strength;
B. very high elongation;
C. strong cementability (with spending sticking or the sticking notion of some contradiction not);
D. good weathering resistance;
E. high stability physical and chemical performance, acid and alkali-resistance, uvioresistant, anti-ozone, not separating oil phase;
F. there is not water-permeable;
G. extremely low second-order transition temperature;
H. wide wide temperature range elasticity.
Another object of the present invention is that a kind of single-component (resisting) moisture curing waterproof coating glue and preparation method thereof will be provided, make it reasonable price and practical.
In order to reach the foregoing invention purpose, single-component of the present invention (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof can contain coreaction product and mixture that component coreactions such as following a, b, c, d, e, f obtain.
A. at least a contain two and or the isocyanate compound of two above isocyanate group, their molecular weight is no more than 1500 usually at 140～400() the optional and combination of TDI, HDI with the most use, MDI, TMDI, IPDI etc., wherein HDI, TMDI, the anti-brownness of IPDI are best;
B. at least aly contain two and or the optional and combination of the polynary polyether alcohols of two above hydroxyls or Viscotrol C.Polynary Aethoxy Sklerol normally 1) polyvalent alcohol and oxyethane and or the optional and combination multipolymer of Ethylene Oxide; 2) tetrahydrofuran (THF) and oxyethane and or the optional and combination multipolymer of propylene oxide; 3) combination 784 glue and 1) 2) and optional, weight-average molecular weight is between 500～5000;
C. at least a 0 to 1 hydroxyl and or the polyesterols resin compound and the mixture of carboxyl of containing.Uncertain contain 1 hydroxyl and or carboxylic compound in the concrete ratio of vibrin in mixture, but contain certainly 0 hydroxyl and or the ratio of carboxyl polyester resin compound in mixture account for the overwhelming majority.And the polyesterols resin compound with following general formula has significant froth breaking and even bubble effect, the effect of dispersion suspension solid particulate or filler:
In the following formula, R=H, CH
3, C
2～C
4Alkyl;
R
1=H, CH
3, N-C
1～C
4, C
2～C
4Alkyl;
R
2=H, CH
3, N-C
2～C
4Alkyl, C
2～C
4Alkyl;
R
3=H, CH
3, C
2～C
4Alkyl;
R
4=C
4～C
25Alkyl, or contain the alkyl of phenanthrene nucleus, terpenyl;
R
5=C
4～C
25Alkyl, or contain the alkyl of phenanthrene nucleus, terpenyl;
m＝1～5;
n＝0～1;
x＞＞y;
D. contain at least a kind of primary amine to and the optional and combination of tertiary amine, poly-primary amine, poly-tertiary amine, these amine are band alkyl with or hydroxyalkyl, as triethylamine, diethylamide, single ethylamine, trolamine, diethanolamine, monoethanolamine, tributylamine etc.And poly-primary amine and or poly-tertiary amine also in addition the alkylene base that do not wait of carbon-bearing atom number or arylene base such as second=amine, to benzene=amine, MOCA etc.
E. at least a UV light absorber that contains reactive hydrogen (normally hydroxyl, amido or carboxyl), oxidation inhibitor, the optional and combination of free radical absorption agent or anti-aging agent.Owing to containing reactive hydrogen thus such additive can enter among the cross-linked network of macromolecular chain with above-mentioned component coreaction, their aerial volatility, the solvability in water have greatly been reduced, improved the health level usage level of the glue of filming of the present invention, expand use range, prolonged work-ing life.Such additive accounts for 0.05～3.0% of prescription total amount; Especially be best with 0.5-1.0%.
F. at least a contain inorganic and or organo-metallic catalyst, be to have very fast or suitable curing speed in order to accelerate to inscribe the glue of stating of filming, the organic and inorganic compound of iron-cobalt-nickel copper and tin normally, such as ferric acetyl acetonade, stannous octoate, December cinnamic acid=butyl tin, cupric chloride (I, II), optional and combination such as copper carboxylate (I, II), addition is for 0.05～3.0% of the prescription total amount, and is best with 0.1～1.0% especially.
Single-component of the present invention (resisting) wet solidification polyurethane waterproof coating resin, the ratio of its isocyanate group and all reactive hydrogen numbers be greater than 1: 1, and normally 1.05～2.2: 1, and preferably 1.25～1.85: 1.
The solvent that the present invention adopts be the dissolving polyethers and or the optional and combination of all kinds of SOLVENTS of vibrin, as the optional and combination of ethyl acetate, acetone, toluene, dimethylbenzene, turpentine, turpentine wet goods.
The present invention can by different purposes and or function, add various properties-correcting agent, as mill base, filler, softening agent, shelf-stable agent etc.
Purpose of the present invention can reach by following measure, and promptly topic is stated the preparation method of the glue of filming, and comprising:
1 polyesterols resin compound and mixture preparation
In the reactor that agitator and reflux, reliever and steam protection are housed, add successively trivalent alcohol and or tetravalent alcohol, as glycerol and or trolamine, rosin (acid), less water and zinc oxide 170～270 ℃ the reaction 0.5～2 hour; 260～290 ℃ were reacted 1～3 hour, and 280～305 ℃ were reacted 0.5～2 hour, added softening agent such as DBP/DOP etc. when cooling to 200～150 ℃, decompression reaction 15～60 minutes, and acid number is less than 30mgKOH/g, and softening agent accounts for 1/4～1/2 of aforementioned total amount.
The preparation of 2 single-components (resisting) wet solidification polyurethane waterproof coating resin
Stir and heating condition under add ester gum with or the product of above-mentioned preparation method 1, polynary Aethoxy Sklerol, organic amine such as TEA or MOCA and filler etc., in 80～150 ℃ of decompression dehydrations 12～120 minutes, controlled temperature adds isocyanate compound or mixture for 60～110 ℃, reacted 1～4 hour, and added catalyzer, inertia mill base and organic solvent and regulate viscosity.Preceding control-NCO/ reactive hydrogen=1.3～2.0 feed intake.
Topic of the present invention is stated the glue of filming and be light yellow or white thick liquid when not being added mill base, about 0.8～the 2.2MP of its tensile strength after the film forming, elongation about 250%, the about 0.5MP of cohesive strength, the artificial aging 500 hours tensile strength conservation rates of weathering resistance that quicken are greater than 70%, and elongation increases relatively.
Topic of the present invention is stated the glue of filming, and has very high chemical physical stability, can be adapted in the environment of soda acid.
Topic of the present invention is stated the glue of filming, owing to contain a spot of residue-NCO group, thereby kept bonding activity, and bonding strength is higher.
The topic of the present invention glue of filming, the most outstanding characteristics, technical advance just of the present invention, advanced in performance being: coating does not have bubble and produces when the single coating thickness is not more than 1.5mm.
It is as follows that topic of the present invention is stated glue and preparation method thereof embodiment that films:
Embodiment 1
In the four-hole boiling flask that agitator and return channel are housed, add rosin (acid) 610 grams; glycerol 59.8 grams; zinc oxide 3 grams, water 10 grams slowly are warmed up to about 180 ℃; it is dissolved finishes; input superheated vapour gas phase protection, steam pressure is 0.3～5.0kPa, slowly is warmed up to about 270 ℃ to react about 0.5 hour; reaction is about 2 hours about 290 ℃, about 305 ℃ anti-about 1 hour.Cool to about 200～150 ℃ add adjacent benzene=formic acid=butyl ester or=monooctyl ester 327 grams, temperature drops to about 180～120 ℃ and reduces pressure-80kPa, can discharging after about 20 minutes, standby.
The product that obtains is vibrin compound and mixture, and acid number is 15～18mgKOH/g, faint yellow transparent adhesive tape.
Embodiment 2
In the four-hole boiling flask that agitator and return channel are housed, add rosin (acid) 1300 grams; trolamine 313 grams; zinc oxide 3.5 grams; water 10 grams; slowly be warmed up to about 150 ℃; its fusing is finished, input superheated vapour gas phase protection, steam pressure 0.3～5kPa; reaction is about 1 hour about 170 ℃; reaction is about 1.5 hours about 260 ℃, and reaction is about 0.5 hour about 280 ℃, cool to about 200～150 ℃ add adjacent benzene=formic acid=butyl ester or=monooctyl ester 400 grams; lower the temperature about 180～120 ℃; reduce pressure-80kPa, can discharging after about about 20 minutes, standby.
The product that obtains is vibrin compound and mixture, acid number 15～18mgKOH/g, light ink green transparent glue.
Embodiment 3
In the there-necked flask of belt stirrer, add Aethoxy Sklerol (330) 75 grams, (220) 60 grams, trolamine 0.5 gram, embodiment 1 or 2 product, 270 grams, anti-aging agent (H) 1.0 gram, filler 120 grams, reducing under 75～100 ℃-80kPa about about 30 minutes, add the TDI55 gram then, 70～90 ℃ of constant temperature 2～4 hours add solvent 80 grams again, can obtain single-component (resisting) wet solidification polyurethane waterproof coating resin.
Embodiment 4
In the there-necked flask of belt stirrer, add Aethoxy Sklerol 103 grams, trolamine 0.5 gram, ester gum 129 grams, softening agent 65 grams, filler 100 grams, anti-aging agent (H) 1.0 grams, stannous octoate 0.1 gram, reducing pressure under 85～150 ℃-80kPa about about 30 minutes, add TDI40 gram then, solvent 60 grams, 75～100 ℃ of constant temperature reaction 2～4 hours, get final product single-component (resisting) wet solidification polyurethane waterproof coating resin.
Embodiment 4 is basic identical with the result of use of embodiment 3.
Claims (12)
1, the present invention is a kind of single-component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof, it is characterized in that comprising following a, b, and c, d, e, reaction product and mixture that f component coreaction obtains:
A. at least a isocyanate compound that contains two or more isocyanate group;
B. at least a contain on two or the polyether alcohols of two above hydroxyls and or Viscotrol C;
C. at least a contain zero to 1 hydroxyl and or the multi-polyester alcohol resin mixture of carboxyl and or compound;
D. few a kind of primary amine to and or tertiary amine and poly-primary amine, poly-tertiary amine;
E. at least a anti-aging agent, oxidation inhibitor or radical terminator, the UV light absorber that contains reactive hydrogen;
F. at least a inorganic and or organo-metallic catalyst, nitrogenous curing urge agent or linking agent;
2, according to a kind of glue of filming of claim 1, the ratio of its isocyanate group number and whole reactive hydrogen numbers was greater than 1: 1.
3, according to a kind of glue of filming of claim 1, its isocyanate compound is characterised in that the optional and combination of its said isocyanic ester, for example toluene=isocyanic ester (2,4 bodies and 2,6 body arbitrary proportions mix), ditan=isocyanic ester, many phenyl polymethine isocyanic ester, contain or not methylic six methynes=isocyanic ester (HDI, TMDI) her sym.-diisopropylideneacetone=isocyanic ester (IPDI) etc.
4, according to the glue of filming of claim 1, it is characterized in that polynary Aethoxy Sklerol be by
A. polyvalent alcohol and oxyethane and or epoxy propane copolymer;
B. tetrahydrofuran (THF) and oxyethane and or epoxy propane copolymer;
C. the optional and combination of above-mentioned a and b.
5,, it is characterized in that polyesterols resin and mixture have following formula by the glue of filming of claim 1
In the following formula, R=H, CH
3, C
2～C
4Alkyl;
R
1=H, CH
3, N-C
1～C
4Alkyl, C
2～C
4Alkyl;
R
2=H, CH
3, N-C
1～C
4Alkyl, C
2～C
4Alkyl;
R
3=H, CH
3, C
2～C
4Alkyl;
R
4=C
4～C25 alkyl contains the alkyl of phenanthrene nucleus, terpenyl;
R
5=C
4～C
25Alkyl contains the alkyl of phenanthrene nucleus, terpenyl;
m＝1～5;
n＝0～1;
x＞＞y
6, by the polyesterols resin of claim 1 to 5, it is characterized in that acid number is below 30mgKOH/g.
7, by the polyesterols resin of claim 1 to 6, its amount is the 1%～80%(weight of glue of filming).
8, by the glue of filming of claim 1, the uncle who relates to and or tertiary amine be the band hydroxyalkyl, the quantity of hydroxyalkyl is between 1 and 3.
9, by the glue of filming of claim 1 to 8, amineization contains the amount of thing in 0.05～3%(weight) between.
10, by the glue of filming of claim 1 to 9, it is characterized in that filler is inorganic or organic, the optional and combination as synthetic resin moulding compound, rubber powder, talcum powder, titanium dioxide etc., its amount is between 5～45%.
11, by the glue preparation method that films of claim 1 to 10, it is characterized in that technology is simple, save the energy, by decompression dehydration, polyisocyanates and Aethoxy Sklerol, polyesterols resin compound and or the Viscotrol C copolyreaction, temperature control is dewatered 85～150 ℃ 12～120 minutes; 60～110 ℃ of 1～4 hour reaction times of copolymerization, preferably 2～3 hours.
12, press the preparation method of claim 1 to 11, the preparation method who also comprises the polyesterols resin, it is characterized in that polyvalent alcohol such as glycerol, trolamine etc. react with rosin (acid) under the zinc oxide katalysis, adopted water vapor to make gas phase protection and product cost is reduced, reaction conditions is 170～270 ℃ of reactions 0.5～2 hour; 260～290 ℃ were reacted 1～3 hour; 280～305 ℃ were reacted 0.5～2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93103057 CN1076712A (en) | 1993-03-14 | 1993-03-14 | Single component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93103057 CN1076712A (en) | 1993-03-14 | 1993-03-14 | Single component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1076712A true CN1076712A (en) | 1993-09-29 |
Family
ID=4984462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93103057 Pending CN1076712A (en) | 1993-03-14 | 1993-03-14 | Single component (resisting) wet solidification polyurethane waterproof coating resin and preparation method thereof |
Country Status (1)
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|---|---|
| CN (1) | CN1076712A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042549C (en) * | 1995-01-09 | 1999-03-17 | 北京市三原建筑粘合材料厂 | Water-proof polyurethane coating film and preparation method thereof |
| CN1087758C (en) * | 1997-05-11 | 2002-07-17 | 化学工业部海洋涂料研究所 | Cavitation erosion preventing paint |
| CN102655929A (en) * | 2009-12-14 | 2012-09-05 | 日本聚氨酯工业株式会社 | Polyurethane-resin-formable composition for film-sealing material, and film-sealing material for module using hollow or flat-film-like fibrous separation film comprising the formable composition |
| CN101809224B (en) * | 2007-10-05 | 2013-11-27 | 东丽株式会社 | Waterproof cloth containing plant-derived component |
| CN104191742A (en) * | 2014-07-31 | 2014-12-10 | 山东浩阳新型工程材料股份有限公司 | Sodium-based bentonite waterproof carpet |
-
1993
- 1993-03-14 CN CN 93103057 patent/CN1076712A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042549C (en) * | 1995-01-09 | 1999-03-17 | 北京市三原建筑粘合材料厂 | Water-proof polyurethane coating film and preparation method thereof |
| CN1087758C (en) * | 1997-05-11 | 2002-07-17 | 化学工业部海洋涂料研究所 | Cavitation erosion preventing paint |
| CN101809224B (en) * | 2007-10-05 | 2013-11-27 | 东丽株式会社 | Waterproof cloth containing plant-derived component |
| CN102655929A (en) * | 2009-12-14 | 2012-09-05 | 日本聚氨酯工业株式会社 | Polyurethane-resin-formable composition for film-sealing material, and film-sealing material for module using hollow or flat-film-like fibrous separation film comprising the formable composition |
| CN102655929B (en) * | 2009-12-14 | 2014-07-23 | 日本聚氨酯工业株式会社 | Polyurethane-resin-formable composition for film-sealing material, and film-sealing material for module using hollow or flat-film-like fibrous separation film comprising the formable composition |
| CN104191742A (en) * | 2014-07-31 | 2014-12-10 | 山东浩阳新型工程材料股份有限公司 | Sodium-based bentonite waterproof carpet |
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