CN1176964C - Preparation and use of elastic high-strength polyurthane prepolymer - Google Patents
Preparation and use of elastic high-strength polyurthane prepolymerInfo
- Publication number
- CN1176964C CN1176964C CNB021379637A CN02137963A CN1176964C CN 1176964 C CN1176964 C CN 1176964C CN B021379637 A CNB021379637 A CN B021379637A CN 02137963 A CN02137963 A CN 02137963A CN 1176964 C CN1176964 C CN 1176964C
- Authority
- CN
- China
- Prior art keywords
- component
- hydroxyl
- polyether
- preparation
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to the preparation and the application of elastic high-strength polyurethane prepolymers. In the present invention, MDI or TDI and MDI are used as diisocyanate, and polyether dibasic alcohol and tribasic alcohol are used as polylol and raw materials to react for preparing the prepolymers; the polylol can be dewatered to a water content of at most 0.05%, and reaction temperature is from 60 to 90 DEG C; the reaction is carried out with heat preservation until the content of NCO is from 5 to 10.5%. The prepolymers are used as a component A containing isocyanate groups and can also be made into dual-component polyurethane paving materials, and a component B containing hydroxy groups matched with the prepolymers is prepared from specific polyether polylol, vulcanizing agents, color filling materials, plasticizing agents and auxiliary agents. Gelatinization is not generated in the process of preparing the prepolymers which can be stably stored. The tensile strength and the wear resistance of the prepared dual-component polyurethane paving materials are improved by 50 to 100% as compared with similar products made of TDI, and moreover, the dual-component polyurethane paving materials have the advantages of no toxicity and no pollution to environment.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of elastic high-strength polyurthane prepolymer.
Background technology
In the dual-component polyurethane system,, normally use 2,4 toluene diisocyanate (hereinafter to be referred as TDI) and polyol reaction to make a kind of prepolymer as the first component that contains isocyanate group.When this prepolymer of preparation, the charging capacity of TDI is excessive, contains the standard value (≤0.7%) that free TDI substantially exceeds environmental requirement in the gained prepolymer.Because the vapour pressure height of TDI (20 ℃, 0.042mmHg), volatile.When preparation and use, human body and environment are all worked the mischief.In addition, when construction, in order to accelerate drying, also must add mercurous and plumbous catalyzer, its add-on mostly is 3～6% of total amount greatly.These mercury, plumbous heavy metal also can increase pollution and harm.4,4 '-diphenylmethanediisocyanate (hereinafter to be referred as MDI).Though, its vapour pressure (30 ℃, about 10
-5MmHg) be lower than TDI, not volatile, toxicity is little.But the reactive behavior of two isocyanate group (hereinafter to be referred as the NCO yl) is identical in this molecule, and activity is too high with polyol reaction the time, and gel easily takes place reaction process, so be difficult to make prepolymer, even if made prepolymer, its package stability is also very poor.Be difficult to suitability for industrialized production and application.
Summary of the invention
The objective of the invention is to, a kind of preparation and application thereof of elastic high-strength polyurthane prepolymer are provided, this preparation method adopts low toxicity, high reactivity MDI, gel does not take place in reaction process, the gained prepolymer is used as the first component that contains isocyanate group in the two ingredient elastic polyurethane system, to human body and environmentally friendly, products obtained therefrom has high strength during construction.
Realize the technical scheme of the object of the invention: a kind of preparation of elastic high-strength polyurthane prepolymer, it is a feedstock production with vulcabond and polyvalent alcohol:
A, raw material
Vulcabond is 4,4 '-diphenylmethanediisocyanate, perhaps 2,4 toluene diisocyanate and 4,4 '-diphenylmethanediisocyanate;
Polyvalent alcohol is polyether Glycols and trivalent alcohol;
Reaction stabilizer;
B, prescription
2,4 toluene diisocyanate 0～19.0%
4,4 '-diphenylmethanediisocyanate 17.0～51.0%
Polyether Glycols 46.0～61.0%
Trivalent alcohol 2.0～13.0%
The reaction stabilizer consumption is 0.01～0.05% of above-mentioned each component total amount, and above-mentioned percentage ratio is weight percentage;
C, preparation technology
1. in reactor, drop into the polyvalent alcohol of formula ratio, stir, heat up, dewater to water content≤0.05%;
2. be lower than 50 ℃ of reaction stabilizers of 1/2～2/3 that add formula ratios, stirring adds the vulcabond of formula ratio again, stir down, 60～90 ℃ react to NCO content be 5～10.5%;
3. be cooled to≤50 ℃, add the reaction stabilizer of surplus and stir evenly filtration, airtight package.
Among the above-mentioned preparation method, described 4,4 '-diphenylmethanediisocyanate be pure solid 4,4 '-diphenylmethanediisocyanate, perhaps for the liquid 4,4 of modification '-diphenylmethanediisocyanate; Described polyether Glycols is that hydroxyl value is the polyether Glycols of 56～300mgKOH/g; Described trivalent alcohol is a trihydroxy-propane, or hydroxyl value is the polyether-tribasic alcohol of 50～500mgKOH/g; Described reaction stabilizer is a phosphoric acid.
Among the above-mentioned preparation method, the dehydration of polyether Glycols and trivalent alcohol can be adopted vacuum hydro-extraction, vacuum tightness 0.4～6mPa, and temperature is 80～120 ℃; Be the solvent refluxing dehydration perhaps with dimethylbenzene.
The polyurethane prepolymer that obtains with above-mentioned preparation method is used as the first component that contains isocyanate group, polyether glycol, vulcanizing agent, filler, pigment, softening agent and auxiliary agent are formed the component B of hydroxyl, during construction, the two mixes by weight 1: 2～4, make the dual-component polyurethane surfacing material, each component of the component B of above-mentioned hydroxyl is by following weight percentage, and is standby behind mixing, grinding, dehydration, the airtight package
Polyether glycol 19.8～43.1%
Vulcanizing agent 1.4～5.4%
Filler 37.9～41.9%
Pigment 2.3～2.7%
Softening agent 14.7～30.0%
Auxiliary agent 0.2～0.6%.
In the component B of the hydroxyl that cooperates with this prepolymer, polyether glycol is polyether Glycols (hydroxyl value 50～100mgKOH/g), polyether-tribasic alcohol (hydroxyl value 50～500mgKOH/g), polyethers tetravalent alcohol (in the hydroxyl value 700～800mgKOH/g) two kinds.
Vulcanizing agent in the component B of hydroxyl is any in the following compound:
Wherein, R is
Or
Softening agent in the component B of hydroxyl is dibutyl phthalate, dioctyl phthalate (DOP), or clorafin.
Auxiliary agent in the component B of hydroxyl is ultraviolet absorbers, antioxidant and mould inhibitor.
Filler in the component B of hydroxyl is the used mineral filler of traditional double component polyurethane system.
Pigment in the component B of hydroxyl is inorganic and/or pigment dyestuff.
Technique effect of the present invention: adopt the raw material, prescription and the preparation technology that stipulate in the technical solution of the present invention, can implement control to two reactive behavioies that are equal to NCO base and polyvalent alcohol in the MDI molecule, make gel does not take place in the whole process of preparation, and the free TDI content of the prepolymer that makes≤0.7%.In addition, the polyurethane prepolymer that makes with the inventive method as the dual-component polyurethane system contain the first component of isocyanate group the time, because, preparing the employed vulcabond of this prepolymer is MDI or MDI and TDI, the symmetrical structure of MDI makes between the formed macromolecular chain packing easily.Therefore, the dual-component polyurethane surfacing material, two-component polyurethane adhesive or the dual-component polyurethane seal gum that make with this prepolymer, it is the product of the same type that vulcabond makes with TDI only that its intensity, wear resistance, elongation etc. all are better than, and when preparing and using this prepolymer, all harmless to human body and environment.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
(1) preparation of polyurethane prepolymer (first component)
A, raw material and prescription see the following form.
| Material name | Specification | Charging capacity (kg) | ||
| Example 1 | Example 2 | Example 3 | ||
| TDI MDI modification MDI | Industrial goods, content 〉=99% industrial goods, white crystals, 38～39 ℃ of industrial goods of fusing point, liquid, NCO content 25～31% | 19.0 - 19.4 | 18.96 18.16 - | - - 51.0 |
| N-220 N-303 TMP | Hydroxyl value 56 ± 4mgKOH/g, industrial goods hydroxyl value 480～500mgKOH/g, industrial goods hydroxyl value 1255mgKOH/g, industrial goods | 54.5 7.1 - | 59.89 - 2.99 | 46.1 - 2.9 |
| Reaction stabilizer phosphoric acid | Reagent or technical grade | 0.02 | 0.03 | 0.04 |
Annotate:
Modification MDI is carbodiimide modification MDI in the table;
N-220 is a polyether Glycols
N-303 is a polyether-tribasic alcohol
TMP is a TriMethylolPropane(TMP)
B, preparation technology
Example 1
1. in having the reactor of vacuum dewatering plant, drop into the N-220 and the N-303 of formula ratio, stir, be warming up to 90 ℃, under vacuum tightness 2 ± 0.5mPa, dewater to water content≤0.05%;
2. be cooled to 45 ℃ of phosphoric acid 0.01kg that add formula ratios 1/2, the TDI and the modification MDI that stir and add formula ratio again stir down, 80 ℃ react to NCO content be 9.5～10%;
3. be cooled to and be lower than 50 ℃, add the phosphoric acid of residual content (0.01kg), stir well even after, filter, airtight package.Its outward appearance is that little Huang is to water white thick liquid, solids constituent 100%.
Example 2
1. in the reactor of taking back the stream device, dropping into the N-220 and the TMP of formula ratio, is reflux solvent with dimethylbenzene, and reflux is dewatered to water content≤0.05%;
2. be cooled to 45 ℃ and add phosphoric acid 0.02kg, the TDI and the MDI powder that stir and add formula ratio again stir down, 80 ℃ react to NCO content be 6 ± 1%;
3. be cooled to and be lower than 50 ℃, add the phosphoric acid of residual content (0.01kg), stir well even after, filter, airtight package.Its outward appearance is an extremely water white thick liquid of little Huang, and solid is divided into 95%.
Example 3
1. in having the reactor of vacuum dewatering plant, drop into the N-220 and the TMP of formula ratio, stir, be warming up to 85 ℃ and under vacuum tightness 1 ± 0.5mPa, dewater to water content≤0.05%;
2. be cooled to 45 ℃, add 0.02Kg phosphoric acid, the modification MDI that stirs and add formula ratio again stirs down, 85 ℃ react to NCO content be 10 ± 0.5%;
3. be cooled to 45 ℃, add residual content phosphoric acid (0.02kg), after stirring, filtration, airtight package.Its outward appearance is that little Huang is to water white thick liquid, solids constituent 95%.
All do not occur gel in the preparation process of example 1～3, package stability (25 ℃) is more than 1 year.
(2) preparation of hydroxyl component B
A, raw material and prescription
| Material name | Specification | Charging capacity (Kg) | |
| No. 1 | No. 2 | ||
| Polyether glycol polyethers tetravalent alcohol (N-403) polyether-tribasic alcohol (N-3050) polyether Glycols (N-220) | Hydroxyl value 770 ± 10mgKOH/g hydroxyl value 56 ± 5mgKOH/g hydroxyl value 56 ± 4mgKOH/g | 0.51 19.33 - | - 17.23 25.84 |
| Vulcanizing agent MOCA | Homemade, industrial goods | 5.33 | 1.4 |
| The white carbon black light calcium carbonate of filler talcum powder kaolin | Industrial goods industrial goods industrial goods industrial goods | 34.89 6.67 0.33 - | - 15.07 - 22.82 |
| The pigment iron oxide red | Industrial goods | 2.67 | 2.37 |
| The softening agent clorafin | Industrial goods | 30.00 | 14.75 |
| Auxiliary agent preventing ultraviolet agent (UV-9) antiaging agent (1010) mould inhibitor (8-hydroxy-quinoline ketone) | Industrial goods industrial goods industrial goods | 0.13 0.07 0.07 | 0.13 0.22 0.17 |
Annotate: the iron oxide red in the table can be according to the user to the requirement of product colour with replacements such as the pigment of other colors such as chrome yellow, phthalocyanine blue, phthalocyanine green, chromoxide greens.
B, preparation technology
Respectively each component in above-mentioned No. 1 and No. 2 prescription is mixed, in sand mill dispersion grinding to fineness in 60～80 mu m ranges, again with after the ordinary method dehydration, airtight package makes the component B of No. 1 and No. 2 hydroxyl respectively.
(3) application of polyurethane prepolymer-making dual-component polyurethane surfacing material
A, preparation
During construction,, mix and stir at 1: 3 by weight with the polyurethane prepolymer (first component) of example 1 and the component B of No. 1 hydroxyl; Perhaps use the polyurethane prepolymer (first component) of example 2 and the component B of No. 2 hydroxyls, mix and stir at 1: 4 by weight; Perhaps use the polyurethane prepolymer (first component) of example 3 and the component B of No. 2 hydroxyls, mix and stir at 1: 4 by weight.They are the dual-component polyurethane surfacing material.
B, construction
Get any in above-mentioned three kinds of surfacing materials, at 20～30 ℃, under the condition of relative humidity 55～75%, paving with artificial or machinery makes overpass road surface, city, golf course walkway, kindergarten's road in concrete, pitch or metallic surface; Perhaps pave and on pitch, concrete stadium runway, make plastic cement race track; Perhaps pave on basketball, vollyball or tennis venue ground, make basketball, vollyball, ground, tennis court, at normal temperatures, do not need to add any catalyzer, can use in 15 days and the nonirritant peculiar smell.
When envrionment temperature is lower than 5 ℃, as long as in the dual-component polyurethane surfacing material, add 0.05% organotin catalysts, perhaps add 3～5% naphthalene acid zinc catalyzer, also can construct and after 15 days, can use.All harmless to environment and human body, the glue-line performance also meets national standard fully.
C, performance
Adopt the ground in the various places of above-mentioned any dual-component polyurethane surfacing material formation, its glue-line physical and mechanical properties all can reach following numerical value after testing:
Tensile strength, MPa is more than 4
Elongation, % is more than 300
Hardness (Shao A), degree 55～65
Tear strength, KN/m 10～15
Compression set, % 4
Shock elasticity, % 20～50
The Taibo abrasion, (mg) 0.7～0.89
Compare with the like product of only making as vulcabond, on tensile strength and wear resisting property, can improve 50～100%, on hardness, tensile strength and three indexs of rebound value, also be better than national standard (GB/T 14833-93) of TDI.In addition, owing to do not need extra catalyst, and free TDI content meets environmental protection standard value (≤0.7%), therefore, and no matter in construction, still in actual use, all to human body and environmentally friendly.
The polyurethane prepolymer that obtains with preparation method of the present invention also can cooperate with the component B of hydroxyl in the technical solution of the present invention makes two-component polyurethane adhesive, and the various rubber grains that are used to bond are made elastic rubber fitting; Elastic floor mat perhaps bonds; Bonding timber, metal or non-metallic material.Can also make the dual-component polyurethane building sealant, perhaps make the dual-component polyurethane water-proof coating.Its cohesive force and sealing effectiveness all are better than only low as like product and the toxicity that vulcabond makes with TDI, and product price is with only suitable as the like product of vulcabond with TDI.
Claims (10)
1, a kind of preparation method of elastic high-strength polyurthane prepolymer, it is a feedstock production with vulcabond and polyvalent alcohol, it is characterized in that:
A, raw material
Vulcabond is 4,4 '-diphenylmethanediisocyanate, perhaps 2,4 toluene diisocyanate and 4,4 '-diphenylmethanediisocyanate;
Polyvalent alcohol is polyether Glycols and trivalent alcohol;
Reaction stabilizer is a phosphoric acid;
B, prescription
2,4 toluene diisocyanate 0～19.0%
4,4 '-diphenylmethanediisocyanate 17.0～51.0%
Polyether Glycols 46.0～61.0%
Trivalent alcohol 2.0～13.0%
The reaction stabilizer consumption is 0.01～0.05% of above-mentioned each component total amount, and above-mentioned percentage ratio is weight percentage;
C, preparation technology
1. in reactor, drop into the polyvalent alcohol of formula ratio, stir, heat up, dewater to water content≤0.05%;
2. be lower than 50 ℃ of reaction stabilizers of 1/2～2/3 that add formula ratios, stirring adds the vulcabond of formula ratio again, stir down, 60～90 ℃ react to NCO content be 5～10.5%;
3. be cooled to≤50 ℃, add the reaction stabilizer of surplus and stir evenly filtration, airtight package.
2, the preparation method of prepolymer according to claim 1, it is characterized in that: described 4,4 '-diphenylmethanediisocyanate be pure solid 4,4 '-diphenylmethanediisocyanate, perhaps for the liquid 4,4 of modification '-diphenylmethanediisocyanate; Described polyether Glycols is that hydroxyl value is the polyether Glycols of 56～300mgKOH/g; Described trivalent alcohol is a TriMethylolPropane(TMP), or hydroxyl value is the polyether-tribasic alcohol of 50～500mgKOH/g.
3, the preparation method of prepolymer according to claim 1 is characterized in that: the dehydration of polyether Glycols and trivalent alcohol can be adopted vacuum hydro-extraction, vacuum tightness 0.4～6mPa, and temperature is 80～120 ℃; Be the solvent refluxing dehydration perhaps with dimethylbenzene.
4, use the application of the polyurethane prepolymer of the described method preparation of claim 1, it is characterized in that: this prepolymer is as the first component that contains isocyanate group, polyether glycol, vulcanizing agent, filler, pigment, softening agent and auxiliary agent are formed the component B of hydroxyl, during construction, the two makes the dual-component polyurethane surfacing material by weight 1: 2～4 mixing, and each component of the component B of above-mentioned hydroxyl is by following weight percentage, standby behind mixing, grinding, dehydration, the airtight package
Polyether glycol 19.8～43.1%
Vulcanizing agent 1.4～5.4%
Filler 37.9～41.9%
Pigment 2.3～2.7%
Softening agent 14.7～30.0%
Auxiliary agent 0.2～0.6%.
5, the application of polyurethane prepolymer according to claim 4 is characterized in that: the polyether glycol in the component B of hydroxyl is two kinds among polyether Glycols hydroxyl value 50～100mgKOH/g, polyether-tribasic alcohol hydroxyl value 50～500mgKOH/g, the polyethers tetravalent alcohol hydroxyl value 700～800mgKOH/g.
6, the application of polyurethane prepolymer according to claim 4 is characterized in that: the vulcanizing agent in the component B of hydroxyl is any in the following compound:
Wherein, R is
Or
7, the application of polyurethane prepolymer according to claim 4 is characterized in that: the softening agent in the component B of hydroxyl is dibutyl phthalate, dioctyl phthalate (DOP), or clorafin.
8, the application of polyurethane prepolymer according to claim 4 is characterized in that: the auxiliary agent in the component B of hydroxyl is ultraviolet absorbers, antioxidant and mould inhibitor.
9, the application of polyurethane prepolymer according to claim 4 is characterized in that: the filler in the component B of hydroxyl is the used mineral filler of traditional double component polyurethane system.
10, the application of polyurethane prepolymer according to claim 4 is characterized in that: the pigment in the component B of hydroxyl is inorganic and/or pigment dyestuff.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021379637A CN1176964C (en) | 2002-07-12 | 2002-07-12 | Preparation and use of elastic high-strength polyurthane prepolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021379637A CN1176964C (en) | 2002-07-12 | 2002-07-12 | Preparation and use of elastic high-strength polyurthane prepolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1392171A CN1392171A (en) | 2003-01-22 |
| CN1176964C true CN1176964C (en) | 2004-11-24 |
Family
ID=4749206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021379637A Expired - Fee Related CN1176964C (en) | 2002-07-12 | 2002-07-12 | Preparation and use of elastic high-strength polyurthane prepolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1176964C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096409B (en) * | 2006-06-26 | 2010-05-12 | 山东东大一诺威聚氨酯有限公司 | Preparation method of polyurethane elastomer for mouse pad |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040249106A1 (en) * | 2003-06-03 | 2004-12-09 | Gindin Lyubov K. | Modified polyurethanes |
| JP5128277B2 (en) | 2004-05-28 | 2013-01-23 | ユニジェン・インコーポレーテッド | Diarylalkanes as potent inhibitors of binuclear enzymes |
| CN101274977B (en) * | 2007-03-29 | 2011-05-25 | 周建明 | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof |
| CN101407571B (en) * | 2007-10-11 | 2010-12-08 | 周建明 | Curing agent toluene diisocyanate and 4,4'-methyl diphenylene diisocyanate mixing prepolymer and preparation thereof |
| CN102504514B (en) * | 2011-10-08 | 2013-08-07 | 广州柏胜化工有限公司 | Polyurethane self-molding material applicable to sports ground and application method thereof |
| CN102746482B (en) * | 2012-07-31 | 2013-12-25 | 河南万里路桥集团有限公司 | Grout material and preparation method thereof for road maintenance |
| CN104745065A (en) * | 2013-12-31 | 2015-07-01 | 上海东大化学有限公司 | High-strength single-component polyurethane waterproofing paint and preparation method thereof |
| CN104178016B (en) * | 2014-09-11 | 2016-05-25 | 浙江春明防水建材有限公司 | The preparation method of environment-friendly type FJS water-repellent paint |
| CN109535385B (en) * | 2018-11-26 | 2020-01-17 | 新疆天地金阳环保新材料有限公司 | Polyurethane prepolymer, preparation method thereof and preparation method of environment-friendly polyurea sports ground surface layer |
| CN111892900A (en) * | 2019-05-05 | 2020-11-06 | 郑州大学 | High-elasticity two-component polyurethane sealant and preparation method thereof |
| CN111073487A (en) * | 2019-12-27 | 2020-04-28 | 河南东方雨虹建筑材料有限公司 | Polyurethane coating and preparation method thereof |
| CN111484598B (en) * | 2020-04-14 | 2022-03-08 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | High-strength single-component tunnel lining structure protective coating |
| CN112375530B (en) * | 2020-11-26 | 2022-10-28 | Sika技术股份公司 | Polyurethane composition with reduced foaming and matte effect |
| CN115850653B (en) * | 2022-09-30 | 2023-08-29 | 广东爱上新材料股份有限公司 | Full TDI prepolymer with low free monomer content for pu runway and preparation method thereof |
-
2002
- 2002-07-12 CN CNB021379637A patent/CN1176964C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096409B (en) * | 2006-06-26 | 2010-05-12 | 山东东大一诺威聚氨酯有限公司 | Preparation method of polyurethane elastomer for mouse pad |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1392171A (en) | 2003-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1176964C (en) | Preparation and use of elastic high-strength polyurthane prepolymer | |
| CN102504514B (en) | Polyurethane self-molding material applicable to sports ground and application method thereof | |
| CN102424721B (en) | Environment friendly plastic slurry for sports field and preparation method thereof | |
| WO2016206636A1 (en) | Polyurethane, modified asphalt and mixture material containing same and road surface structure | |
| CN102770599B (en) | Composite road surface structure | |
| CN104693783B (en) | A kind of bituminous paving two-component normal temperature cure gap-grouting material | |
| CN104559734A (en) | Double-component chemical-reaction thixotropic polyurethane waterproof paint and preparation method thereof | |
| CN102585147A (en) | Polyurethane elastic body composition for engineering equipment | |
| CN1281702C (en) | Preparing process and application of wet-solidifying single-component polyurethane adhesive | |
| CN1552999A (en) | Environmental protection weeping plastic track | |
| CN1730594A (en) | Direct-adhesion type polyurethane seal gum | |
| CN102040723A (en) | Polyurethane elastomer composition for shoe material | |
| CN107141773A (en) | A kind of environment-friendly polyurethane plastic cement race track and preparation method thereof | |
| CN1290927C (en) | Water solution treatment process of polyurethane elastomer to make plastic track | |
| CN1310993C (en) | Water curable polyurethane compositions and uses thereof | |
| KR101471446B1 (en) | Ecofriendly porous binder composition for polymer concrete | |
| JP4225488B2 (en) | Environment-friendly curable composition and method for producing the same | |
| CN101245223A (en) | Environment protection type polyurethane non-particle spray coating material for play ground layer and manufacture method thereof | |
| CN1269864C (en) | Environmentally friendly track rubber, and its production method and track construction method using same | |
| KR101144140B1 (en) | Environmental-friendly elastic paving material and method of preparing the paving material | |
| CN107090131A (en) | A kind of wear-resisting antiskid plastic cement race track and preparation method | |
| CN110527482A (en) | Railway ballastless track special dual-component filleting waterproof gasket cement and preparation method thereof | |
| KR101480802B1 (en) | Method for producing of waterborne urethane binder for surface coating materials | |
| JP2010121350A (en) | Polyurethane composition for elastic pavement | |
| CN108047919A (en) | A kind of double-composition polyurethane waterproof paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |