CN101633719B - Normal-temperature solidification polyurethane elastomer waterproof material and preparation method thereof - Google Patents
Normal-temperature solidification polyurethane elastomer waterproof material and preparation method thereof Download PDFInfo
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- CN101633719B CN101633719B CN 200910173018 CN200910173018A CN101633719B CN 101633719 B CN101633719 B CN 101633719B CN 200910173018 CN200910173018 CN 200910173018 CN 200910173018 A CN200910173018 A CN 200910173018A CN 101633719 B CN101633719 B CN 101633719B
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Abstract
The invention discloses a normal-temperature solidification polyurethane elastomer waterproof material and a preparation method thereof. The polyurethane waterproof material comprises a component A and a component B. Proportioning by weight percent, the component A is an isocyanate prepolymer with the content of 4-15% of isocyanic acid radical NCO; the component B comprises 0-65% of polyether glycol with the degree of functionality of 2-3 and the molecular weight of 1,000-5,000, 0.6-1.2% of organic bismuth catalyst, 20-27.5% of polybasic amine, 0-1.3% of antioxidant and 12.5-71.9% of plasticizer. The component A and the component B are mixed according to the weight ratio of 100(60-81); the material obtained by room-temperature solidification has the mechanical properties that the tensile strength is 15-35MPa, the tearing strength is 44-62N/mm, the breaking elongation rate is 405-840%, and the Shao' hardness is 75-90A.
Description
Technical field
The present invention relates to buildings waterproof impervious material and preparation thereof, particularly normal-temperature solidification polyurethane elastomer waterproof material and preparation method thereof.
Background technology
Polyurethane elastomer can be used as water-proof material; Have multiple good performances such as wear-resisting, oil resistant, acid and alkali-resistance, hydrolysis and pharmaceutical chemicals and boundary of works area be wide; Get into China water-proof material market in the seventies in last century, be widely used in roofing, underground works and kitchen and toilet, also be widely used in heavy construction field such as heavily loaded road and bridge, high speed railway track L.C. etc.; Having obtained the excellent waterproof effect, is one of water-proof material product of the present emphasis popularization of China.
Polyurethane waterproof material is called polyurethane water-proof paint or polyurethane film-coated water-proof material again, is a kind of chemical reaction type coating, according to composition of filming and curing mechanism, is divided into two kinds of forms of single component and polycomponent, how to use with the two-pack form.Bicomponent polyurethane coating generally is made up of isocyanate prepolymer and hydroxy-containing resin two portions.
Polyurethane water-proof paint all is a curing molding under the normal temperature generally, and elastomeric mechanical property receives the influence of catalyzer very big after the moulding.At present; The catalyzer that the domestic production polyurethane water-proof paint is selected for use all is the organic tin catalyzer; Disclose a kind of bicomponent high-strength degree polyurethane water-proof paint like CN101100582A, CN101113286A discloses a kind of polyurethane water-proof paint that does not contain coal tar and toluene solvant, and CN101113288 A discloses the working method of polyurethane water-proof paint; The catalyzer that uses in these materials all is dibutyl tin laurate or stannous octoate; The toxicity of such catalyzer is bigger, is unfavorable for environmental protection, and production and workmen's health is brought very big harm.
Summary of the invention
The technical problem that the present invention will solve provides a kind of environment protection type polyurethane elastomer water-proof material, overcomes the harm of using above-mentioned catalyzer that human body is brought.
Another technical problem that the present invention will solve provides a kind of method for preparing this polyurethane elastomer waterproof material.
Polyurethane waterproof material of the present invention is made up of A, B two-pack.By weight percentage, the A component is that isocyano (NCO) content is 4%～15% isocyanate prepolymer; The B component is that 2～3 molecular weight are that 1000～5000 polyether glycol, 0.6%～1.2% organic bismuth catalyst, 20%～27.5% polyamine, 0～1.3% oxidation inhibitor and 12.5%～71.9% softening agent are formed by 0～65% functionality.A, B component are mixed self-vulcanizing gained material mechanical performance: tensile strength 15～35MPa, tear strength 44～62N/mm, elongation at break 405%～840%, hardness (Shao Shi) 75A～90A by weight 100/60～81.
The A component can by tolylene diisocyanate (TDI) and polyether glycol and the small molecules glycol is synthetic makes.Wherein polyether glycol is selected from that functionality is 2～3, molecular weight is in 1000～5000 the polyoxytrimethylene ether one or more; The small molecules glycol is 1, one or more in 4-butyleneglycol (BDO), TriMethylolPropane(TMP) (TMP), dipropylene glycol (DPG), the glycol ether (DEG).
A component compound method is: the polyether glycol and the small molecules glycol of metering are added in the reaction kettle; Be heated to 100～110 ℃, behind the 2～3h that dewaters under the vacuum, will expect temperature drop to 40～60 ℃; The TDI that slowly adds metering; Behind reinforced the end, under nitrogen protection,, be cooled to normal temperature in 80～100 ℃ of reaction 2～3h.
Polyether glycol comprises that molecular weight is one or more in 1000～5000 the polyoxytrimethylene ether glycol in the B component; Organic bismuth catalyst can be the various organic acid salts of bismuth, mainly provides metals ion, and organic acid is not had special qualification, like in isocaprylic acid bismuth, naphthenic acid bismuth, the quinane acid bismuth one or more; Polyamine comprises 3,3 two chloro-, 4,4 diaminodiphenyl-methanes (MOCA), 3; 5-diformazan sulfenyl-2,4-tolylene diamine, 3,5-diformazan sulfenyl-2; 6-tolylene diamine (E-300), 2,4-diamino--5-sulfydryl toluene (TX-1), 2,4-diamino--3; 5-diformazan sulfenyl chlorobenzene (TX-2), 2, one or more in 4-diamino--3-methylthio group-5-propyltoluene (TX-3) etc.; Oxidation inhibitor preferred four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010) or 2, one or both in the 6-toluene di-tert-butyl phenol (BHT); Softening agent comprises DOP, dimethyoxethyl ph-, diethyl phthalate, 2,2,4-trimethylammonium-1, one or more in the 3-pentanediol diisobutyrate (TXIB).
The preparation method of B component is that oxidation inhibitor, catalyzer, softening agent etc. stir and promptly get with polyether Glycols, polyamine chainextender.Polyether Glycols need be heated to 100～110 ℃ before adding, and the 2～3h that dewaters under the vacuum carries out preparatory processed.
Polyurethane elastomer waterproof material of the present invention can add some solid packings such as coal ash, lime carbonate, talcum powder etc. to reduce cost in when construction in material; Amount of filler can account for 10～50% weight parts; The tensile strength of material can satisfy the requirement of GB GB/T19250-2003 " polyurethane water-proof paint " still greater than 6Mpa.
Beneficial effect of the present invention has been to adopt nontoxic organo-bismuth class catalyzer to replace deleterious organic tin catalyzer, to producing and workmen safer, helps environmental protection.Simultaneously, such catalyzer can make the mechanical property of polyurethane elastomer improve fast at normal temperatures, can guarantee job schedule and specification of quality.
Another characteristic of the present invention is that constructional method is flexible, adds behind the filler product and still can show characteristics such as HS, hydrolysis, ageing-resistant, long service life.
The prepared polyurethane waterproof material of the present invention has excellent wear-resisting, oil resistant, acid and alkali-resistance, hydrolysis and pharmaceutical chemicals performance, and boundary of works area is extensive, can be used for fields such as roofing, underground works and toilet, heavily loaded road and bridge waterproof.
Embodiment
Below in conjunction with embodiment the present invention is further specified, be not limited to the present invention.
Embodiment 1
A component: be in 1000 64 parts of the polyoxypropyleneglycols and 6.5 parts of adding reaction kettles of dipropylene glycol (DPG) with molecular weight; Be warmed up to 100～110 ℃, cool to 50 ℃ behind the vacuum hydro-extraction 3h, add 29.5 parts of TDI; Between 80～100 ℃, be incubated 2h, obtain NCO content and be 12% performed polymer.
The B component: with 52 parts of molecular weight is that 2000 polyoxypropyleneglycol adds in the reaction kettle, behind 100～110 ℃ of vacuum hydro-extraction 3h, adds 3; 3 '-two chloro-4,4 '-10 parts of ditans (MOCA), treat that it has melted the back fully and has added 2; 4-diamino--3,6 parts of 5-diformazan sulfenyl chlorobenzenes (TX-2), softening agent 2; 2,4-trimethylammonium-1,10 parts of 3-pentanediol diisobutyrates (TXIB); 1 part of antioxidant 1010 (four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), catalyst rings alkanoic acid bismuth stirs for 0.9 part and processes.The AB component is the casting and constructing of A/B=100/81 mixing by weight proportion at normal temperatures.The AB component is the casting and constructing of A/B=100/81 mixing by weight proportion at normal temperatures.
7 days main physicalies of material cured are following:
Tensile strength 35.0MPa
Elongation at break 565%
Tear strength 61.4N/mm
Hardness (Shao Shi) 80A
Embodiment 2
The preparation of A, B component is with embodiment 1.The AB component when mixing cast according to A/B/ coal ash=100/81/120 mixed.7 days physical properties of this material cured can be as follows:
Tensile strength 9.1MPa
Elongation 405%
Tear strength 50.7N/mm
Hardness (Shao Shi) 90A
Embodiment 3
With molecular weight is that 1000 polyoxypropyleneglycol is 50 parts of 2000 polyoxypropyleneglycols with molecular weight for 50 parts; In 8 parts of adding reaction kettles of glycol ether (DEG), be warmed up to 100～110 ℃, cool to 50 ℃ behind the dehydration 3h under the vacuum; Add 28 parts of tolylene diisocyanates; Reaction is 2 hours between 80～100 ℃, obtains NCO content and be 4.5% performed polymer, and this is the A component.The B component is with 3,5-diformazan sulfenyl-2, and 13 parts of 4-tolylene diamine chainextenders, 3,5-diformazan sulfenyl-2,10 parts of 6-tolylene diamines, 60 parts of plasticizer phthalic acid dioctyl esters, stirring after 0.5 part of priority of catalyzer isocaprylic acid bismuth adds in the reaction kettle obtains.With the A/B=100/60 mixed, construction does not have the foaming phenomenon on moist basal plane at normal temperatures.
7 days physical properties of this material cured can be as follows:
Tensile strength 15.1MPa
Elongation 840%
Tear strength 44.5N/mm
Hardness (Shao Shi) 75A
Claims (4)
1. a polyurethane elastomer waterproof material is made up of A, B two-pack; By weight percentage; The A component is that the synthetic isocyano-content that makes of tolylene diisocyanate and polyether glycol and small molecules glycol is 4%～15% isocyanate prepolymer; Polyether glycol is selected from that functionality is 2～3, molecular weight is in 1000～5000 the polyoxytrimethylene ether one or more; The small molecules glycol is 1, one or more in 4-butyleneglycol (BDO), dipropylene glycol (DPG), the glycol ether (DEG); The B component by 0～65% molecular weight be in 1000～5000 the polyoxytrimethylene ether glycol one or more, 0.6～1.2% organic bismuth catalyst, 20%～27.5% polyamine, 0～1.3% oxidation inhibitor and 12.5%～71.9% softening agent form, A, B component are mixed self-vulcanizing by weight 100/60～81; Wherein polyamine is meant 3,3 two chloro-, 4,4 diaminodiphenyl-methanes, 3; 5-diformazan sulfenyl-2,4-tolylene diamine, 3,5-diformazan sulfenyl-2; 6-tolylene diamine, 2,4-diamino--5-sulfydryl toluene, 2,4-diamino--3; 5-diformazan sulfenyl chlorobenzene, 2, one or more in 4-diamino--3-methylthio group-5-propyltoluene.
2. described polyurethane elastomer waterproof material of claim 1, it is characterized in that material cured after mechanical property be: tensile strength 15～35MPa, tear strength 44～62N/mm, elongation at break 405%～840%, shore hardness 75～90A.
3. the described polyurethane elastomer waterproof material of claim 2 is characterized in that when construction, in material, adding solid packing, and amount of filler can account for 10～50% weight parts.
4. the preparation method of the described polyurethane elastomer waterproof material of claim 2 comprises:
A component: the polyether glycol and the small molecules glycol of metering are added in the reaction kettle, be heated to 100～110 ℃, behind the 2～3h that dewaters under the vacuum; To expect temperature drop to 40～60 ℃, slowly add the TDI of metering, behind reinforced the end; Under nitrogen protection,, be cooled to normal temperature in 80～100 ℃ of reaction 2～3h;
The B component: with polyether Glycols, polyamine, oxidation inhibitor, catalyzer, softening agent mixing and stirring;
Wherein: the polyether glycol of A component is selected from that functionality is 2～3, molecular weight is in 1000～5000 the polyoxytrimethylene ether one or more; The small molecules glycol is 1, one or more in 4-butyleneglycol BDO, dipropylene glycol, the glycol ether; Polyether glycol is meant that molecular weight is one or more in 1000～5000 the polyoxytrimethylene ether glycol in the B component; Organic bismuth catalyst is meant one or more in isocaprylic acid bismuth, naphthenic acid bismuth, the quinane acid bismuth; Polyamine is meant 3,3 two chloro-, 4,4 diaminodiphenyl-methanes, 3; 5-diformazan sulfenyl-2,4-tolylene diamine, 3,5-diformazan sulfenyl-2; 6-tolylene diamine, 2,4-diamino--5-sulfydryl toluene, 2,4-diamino--3; 5-diformazan sulfenyl chlorobenzene, 2, one or more in 4-diamino--3-methylthio group-5-propyltoluene etc.; Oxidation inhibitor is meant four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or 2, one or both in the 6-toluene di-tert-butyl phenol; Softening agent is meant DOP, dimethyoxethyl ph-, diethyl phthalate, 2,2,4-trimethylammonium-1, one or more in the 3-pentanediol diisobutyrate.
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| CN101633719B true CN101633719B (en) | 2012-02-29 |
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Families Citing this family (13)
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| CN102212307A (en) * | 2010-04-02 | 2011-10-12 | 上海东方雨虹防水技术有限责任公司 | Double-component polyurethane waterproofing paint and preparation method thereof |
| DE102010019504A1 (en) * | 2010-05-06 | 2011-11-10 | Bayer Materialscience Ag | Polyisocyanate prepolymers and their use |
| CN102010654A (en) * | 2010-11-16 | 2011-04-13 | 北方涂料工业研究设计院 | Method for preparing environmental-friendly high-performance polyurethane waterproof paint |
| CN102181037B (en) * | 2011-03-27 | 2012-08-08 | 黎明化工研究院 | Method for preparing 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI)-based thermoplastic polyurethane elastomer |
| CN102516493B (en) * | 2011-11-30 | 2013-09-11 | 上海东大化学有限公司 | Polyurethane strengthening water shutoff material special for mining and preparation method thereof |
| CN103627310B (en) * | 2013-11-01 | 2016-01-06 | 华南理工大学 | A kind of preparation method of spraying surface of environment-protecting polyurethane plastic cement race track |
| CN103709923B (en) * | 2013-12-18 | 2016-08-17 | 黎明化工研究设计院有限责任公司 | A kind of wear-resisting spraying polyurethane resin combination and preparation method thereof and construction method |
| CN104650315A (en) * | 2015-02-16 | 2015-05-27 | 中国海洋石油总公司 | Compound polyurethane elastomer composite and preparation method thereof |
| CN105820310A (en) * | 2016-04-07 | 2016-08-03 | 苏州绿朗新材料科技有限公司 | NCO prepolymer as well as preparation method and use thereof |
| CN109912760A (en) * | 2017-12-13 | 2019-06-21 | 上海优迈材料科技有限公司 | A kind of oil-resisting type floor-cleaning machine water suction adhesive tape and preparation method thereof |
| CN111909344B (en) * | 2020-08-12 | 2022-04-22 | 上海博盛聚氨酯制品有限公司 | Normal-temperature polyurethane elastomer for rails of future urban rail buses, and preparation method and application thereof |
| CN113831492B (en) * | 2021-09-18 | 2024-01-26 | 北京九州一轨环境科技股份有限公司 | Preparation method of polyurethane elastomer for steel rail energy consumption piece, polyurethane elastomer and energy consumption piece |
| CN115725230A (en) * | 2022-12-13 | 2023-03-03 | 上海东大化学有限公司 | Environment-friendly high-strength two-component coating and preparation method thereof |
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