CN103045153B - Bi-component polyurethane adhesive of a kind of resistance to acid liquid corrosion and its preparation method and application - Google Patents
Bi-component polyurethane adhesive of a kind of resistance to acid liquid corrosion and its preparation method and application Download PDFInfo
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- CN103045153B CN103045153B CN201210468595.4A CN201210468595A CN103045153B CN 103045153 B CN103045153 B CN 103045153B CN 201210468595 A CN201210468595 A CN 201210468595A CN 103045153 B CN103045153 B CN 103045153B
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Abstract
The invention discloses bi-component polyurethane adhesive of a kind of resistance to acid liquid corrosion and its preparation method and application, it is characterized in that: mixed by component A and B component, is 0.8-20:1 according to weight ratio A:B; Wherein said component A is composed of the following components by weight: polyether glycol 30-90, chainextender 1-20, acid resistance filler 10-50, softening agent 10-50, hydrolysis stabilizer 0.5-5, water-retaining agent 0.5-2 part, adhesion promoter 0.5-5, thixotropic agent 1-10 part, catalyzer 0.01-0.2; Described B component is that polyisocyanate resin 10-82 or described B component are composed of the following components by weight: polyisocyanate resin 10-80, softening agent 0.1-20.Then preparation component A and B component mix respectively.The bi-component polyurethane adhesive of described resistance to acid liquid corrosion has higher intensity and hardness, the excellent performance of resistance to acid liquid corrosion, and bonding strength is high, is suitable for the bonding use of acid solution environment, can in the application in desulfuration chimney, acid solution treating pond field.
Description
Technical field
The present invention relates to a kind of chemical adhesive, particularly relate to bi-component polyurethane adhesive of a kind of resistance to acid liquid corrosion and its preparation method and application.
Background technology
The application of polyurethane adhesive is familiar with gradually.Urethane can regard a kind of segmented copolymer containing soft chain segment and hard segment as.Hard section is made up of polyisocyanates or itself and small molecule chain extender, and hard segment molecule provides shearing, stripping strength and resistance toheat, and soft section is provided by oligomer polyol, normally polyethers and polyester polyol, has the characteristics such as shock-resistant, antifatigue.Regulate the structure of in polyurethane molecular hard, soft section, the satisfactory various structures polyurethane adhesive of intensity can be obtained.
Current, polyurethane adhesive due to its uniqueness mechanical property and processing performance, be obtained in a lot of field and develop fast, be especially widely used in some waterproof field.But due to polyurethane adhesive, common polyurethane adhesive does not tolerate the corrosion of acid solution, limit polyurethane adhesive under acid environment, such as the use in the field such as desulfuration chimney, acid solution treating pond.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of bi-component polyurethane adhesive and its preparation method and application, has higher intensity and hardness, and resistance to acid liquid corrosion performance can be excellent, and bonding strength is high, is suitable for the bonding use of acid solution environment.
Technical problem to be solved by this invention is achieved through the following technical solutions:
A bi-component polyurethane adhesive for resistance to acid liquid corrosion, is characterized in that: mixed by component A and B component, is 0.8-20: 1 according to weight ratio A: B;
Wherein said component A is composed of the following components by weight: polyether glycol 30-90, chainextender 1-20, acid resistance filler 10-50, softening agent 10-50, hydrolysis stabilizer 0.5-5, water-retaining agent 0.5-2 part, adhesion promoter 0.5-5, thixotropic agent 1-10 part, catalyzer 0.01-0.2;
Described B component is that polyisocyanate resin 10-82 or described B component are composed of the following components by weight: polyisocyanate resin 10-80, softening agent 0.1-20.
Be preferably 1-10: 1 according to weight ratio A: B.
Polyether glycol described in component A comprises functionality and is 2-4 and molecular weight is the one in the polyoxypropylene polyol of 300-20000;
Described chainextender is di-alcohols;
Described acid resistance filler is silicon powder, mica powder or barium sulfate;
Described softening agent is phthalate;
Described hydrolysis stabilizer is Carbodiimides material;
Described adhesive power promotor is silane coupling agent;
Described water-retaining agent is p-Methyl benzenesulfonyl isocyanate or oxazole alkanes moisture scavenger;
Described thixotropic agent is aerosil or organobentonite;
Described catalyzer is organic tin catalyzer.
Polyisocyanate resin described in B component is polyisocyanates and derivative thereof; Described softening agent is phthalate.
Described di-alcohols is Isosorbide-5-Nitrae butyleneglycol, ethylene glycol, Diethylene Glycol, 1, a kind of in 6 hexylene glycols, HQEE (quinhydrones-bis-(B-hydroxyethyl) ether) or its arbitrarily between mixture;
Described phthalate is dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate or Di Iso Decyl Phthalate; Preferred dibutyl phthalate or diisononyl phthalate;
Described silane coupling agent is N-(β mono-aminoethyl) γ mono-aminopropyl trimethoxysilane, γ mono-glycidyl ether oxygen propyl trimethoxy silicane, γ mono-aminopropyl trimethoxysilane, γ mono-aminopropyl triethoxysilane or γ monomethyl propylene phthalein oxygen propyl trimethoxy silicane;
Described organic tin catalyzer is dibutyl tin laurate, stannous octoate or dibutyltin mercaptide.
Described polyisocyanates and derivative thereof are tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate, liquefied mdi (diphenylmethanediisocyanate), TDI (tolylene diisocyanate) tripolymer, HDI (hexamethylene diisocyanate) biuret or HDI (hexamethylene diisocyanate) tripolymer; Preferred polymethylene multi-phenenyl isocyanate or liquefied mdi (diphenylmethanediisocyanate);
Described phthalate is dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate or Di Iso Decyl Phthalate, preferred dibutyl phthalate or diisononyl phthalate.
The granularity of silicon powder, mica powder or barium sulfate is 100 order-15000 orders.
The preparation method of the bi-component polyurethane adhesive of described resistance to acid liquid corrosion, is characterized in that: prepare component A and B component respectively, wherein component A is prepared from by following steps:
A () at room temperature sequentially adds polyether glycol, chainextender, softening agent blended 10-90 minute under vacuum protection in stirring tank;
B () adds acid resistance filler, thixotropic agent, hydrolysis stabilizer, adhesion promoter, water-retaining agent, vacuum stirring 30 minutes;
C () adds catalyzer, vacuum stirring 10-90 minute;
(d) carry out degassed after, the component A product of paste can be obtained;
Be prepared from as follows when wherein B component is mixture:
(a) at room temperature in stirring tank order add polyisocyanate resin, softening agent, blended 15-60 minute under vacuum protection, obtain finely dispersed B component product;
Component A and B component are proportionally used in combination.
The stirring tank of preparation component A is dual shaft planetary stirring tank, the enamel reaction stirring tank that preparation B component is.
The application of bi-component polyurethane adhesive in desulfuration chimney, acid solution treating pond field of described resistance to acid liquid corrosion.
Tool of the present invention has the following advantages:
The bonding system of two component polyurethane of the application, mainly improves cementability and hydrolytic resistance from the following aspects:
(1) anti-hydrolytic performance and the good polyol component of acid corrosion-resistant performance is adopted, in two component adhesive described by the application, polyol component is polyoxypropylene polyol, it has good hydrophobic performance, and its ehter bond has good resistance to acid liquid corrosion performance simultaneously;
(2) adopt glycol chain extender, improve the crystal property of system, reach the object improving acid corrosion-resistant performance;
(3) adopt acidproof filler, acid resistance filler itself has very high acid corrosion-resistant ability, after adding system, can improve modulus and the degree of compactness of system, improve the acid corrosion-resistant performance of system equally;
(4) introduce hydrolysis stabilizer, the present invention adopts Carbodiimides material.The corrosion in acid solution of urethane, follows the process of the hydrolysis of acid solution Promotion system, after adding hydrolysis stabilizer, can slow down or lower the hydrolytic process of system, thus reach the object of raising system acid corrosion-resistant ability;
(5) adhesive power promotor is added.Adhesive power promotor used in the present invention is organo-silicon coupling agent, defines hydrophobic chemical adhesive layer, while raising adhesiveproperties, also can improve the acid corrosion-resistant ability of glue-line;
(6) in formulating of recipe, all selecting materials all adopts hydrophobic raw material, reduces the perviousness of acid solution in system, thus reaches the object of raising system acid corrosion-resistant ability.
Embodiment
Embodiment 1
Precise raw material (Kg):
Component A: the polyether glycol 2028 of molecular-weight average 4000 is 90, Isosorbide-5-Nitrae butyleneglycol 4, silicon powder (400 order) 15, dibutyl phthalate 30, N, N '-two (2,6-diisopropyl phenyl) carbodiimide) 1, oxazolidine water-retaining agent 1, γ mono-glycidyl ether oxygen propyl trimethoxy silicane 2, white carbon black 5, dibutyl tin laurate 0.1;
B component: polyisocyanate resin 80, dibutyl phthalate 20.
Prepared by the present embodiment:
Component A: during preparation, at room temperature in dual shaft planetary stirring tank, order adds polyether glycol 2028, butyleneglycol, dibutyl phthalate, under vacuum protection blended 10 minutes; Add silicon powder (400 order), N, N '-two (2,6-diisopropyl phenyl) carbodiimide, white carbon black, oxazolidine water-retaining agent, γ mono-glycidyl ether oxygen propyl trimethoxy silicane, vacuum stirring 30 minutes; Add dibutyltin dilaurate catalyst, vacuum stirring 10 minutes; Carry out degassed after, the component A product of paste can be obtained;
B component: during preparation, at room temperature enamel reaction stirring tank, order adds polyisocyanate resin and dibutyl phthalate, under vacuum protection blended 15 minutes, obtains B component product.
Component A and B component used in combination according to the ratio of weight ratio 6: 1.
The bi-component polyurethane adhesive of above-mentioned resistance to acid liquid corrosion is applied in desulfuration chimney, acid solution treating pond field.
Embodiment 2
Precise raw material (Kg):
Component A: the polyether glycol 3050 of molecular-weight average 3000 is 80,1,6 hexylene glycols 10, barium sulfate (2000 order) 50, diisononyl phthalate 20, polycarbodiimide 2, oxazolidine water-retaining agent 2, γ monomethyl propylene phthalein oxygen propyl trimethoxy silicane 3, white carbon black 4, stannous octoate 0.05
B component: polyisocyanate resin 75, dibutyl phthalate 15;
Prepared by the present embodiment:
Component A: during preparation, at room temperature in dual shaft planetary stirring tank, order adds polyether glycol 3050,1,6 hexylene glycols, diisononyl phthalate, under vacuum protection blended 10 minutes; Add barium sulfate (2000 order), diisononyl phthalate, polycarbodiimide, white carbon black, oxazolidine water-retaining agent, γ monomethyl propylene phthalein oxygen propyl trimethoxy silicane, vacuum stirring 30 minutes; Add stannous octoate catalyst, vacuum stirring 10 minutes, carry out degassed after, the component A product of paste can be obtained.
B component: during preparation, at room temperature enamel reaction stirring tank, order adds polyisocyanate resin, dibutyl phthalate, under vacuum protection blended 15 minutes, obtains B component product.
Component A and B component used in combination according to the ratio of weight ratio 4: 1.
After embodiment and currently available products solidify, performance comparison is as shown in the table:
Wherein comparative example: market product is similar dual-component polyurethane adhesive.
From the result of reality test, embodiment 1 and embodiment 2 are after 90 days 10% sulfuric acid corrosions, and tensile strength and retention rate thereof are still higher, are obviously better than market like product.
Hardness: by GB/T531.1-2008 " vulcanized rubber and thermoplastic elastomer penetration hardness test method first part: the clear young that hardness of Shore durometer method " evaluation hardness.
Tensile strength: evaluate tensile strength by GB/T528-1998 " mensuration of vulcanized rubber and thermoplastic elastomer tensile stress-strain performance ".
Shearing resistance: evaluate shearing resistance by GB-T7124-2008 " mensuration (rigid material is to rigid material) of tackiness agent tensile shear strength ", sandblasting grinding process is made on steel substrate surface.
The bi-component polyurethane adhesive of above-mentioned resistance to acid liquid corrosion is applied in desulfuration chimney, acid solution treating pond field.
Embodiment 3
Precise raw material (Kg):
Component A is composed of the following components by weight: polyether glycol 30, chainextender 1, acid resistance filler 10, softening agent 10, hydrolysis stabilizer 0.5, water-retaining agent 0.5, adhesion promoter 0.5, thixotropic agent 1, catalyzer 0.01; B component is polyisocyanate resin 10, softening agent 0.1.
Wherein polyether glycol is polyoxypropylene polyol, chainextender is Diethylene Glycol, acid resistance filler is mica powder, softening agent is diisononyl phthalate, and hydrolysis stabilizer is polycarbodiimide, and water-retaining agent is p-Methyl benzenesulfonyl isocyanate, adhesion promoter is N-(β mono-aminoethyl) γ mono-aminopropyl trimethoxysilane, thixotropic agent is organobentonite, and catalyzer is stannous octoate, and polyisocyanate resin is polymethylene multi-phenenyl isocyanate.
Preparation method with embodiment 1, wherein component A and B component used in combination according to the ratio of weight ratio 0.8: 1.
The bi-component polyurethane adhesive of above-mentioned resistance to acid liquid corrosion is applied in desulfuration chimney, acid solution treating pond field.
Embodiment 4
Precise raw material (Kg):
Component A is composed of the following components by weight: polyether glycol 90, chainextender 20, acid resistance filler 50, softening agent 50, hydrolysis stabilizer 5, water-retaining agent 2, adhesion promoter 5, thixotropic agent 10, catalyzer 0.2;
B component is composed of the following components by weight: polyisocyanate resin 80, softening agent 20.
Wherein polyether glycol is polyoxypropylene polyol, chainextender is HQEE, acid resistance filler is mica powder, softening agent is dibutyl phthalate, and hydrolysis stabilizer is polycarbodiimide, and water-retaining agent is oxazolidine water-retaining agent, adhesion promoter is γ mono-glycidyl ether oxygen propyl trimethoxy silicane, thixotropic agent is organobentonite, and catalyzer is dibutyltin mercaptide, and polyisocyanate resin is liquefied mdi.
Preparation method with embodiment 1, wherein component A and B component used in combination according to the ratio of weight ratio 20: 1.
The bi-component polyurethane adhesive of above-mentioned resistance to acid liquid corrosion is applied in desulfuration chimney, acid solution treating pond field.
Embodiment 5
Precise raw material (Kg):
Component A is composed of the following components by weight: polyether glycol 60, chainextender 10, acid resistance filler 30, softening agent 25, hydrolysis stabilizer 2, water-retaining agent 1.2, adhesion promoter 3, thixotropic agent 5, catalyzer 0.1; B component is polyisocyanate resin 82.
Wherein polyether glycol is polyoxypropylene polyol, chainextender is HQEE, acid resistance filler is mica powder, softening agent is dibutyl phthalate, and hydrolysis stabilizer is polycarbodiimide, and water-retaining agent is oxazolidine water-retaining agent, adhesion promoter is γ monomethyl propylene phthalein oxygen propyl trimethoxy silicane, thixotropic agent is organobentonite, and catalyzer is dibutyltin mercaptide, and polyisocyanate resin is diphenylmethanediisocyanate.
Preparation method with embodiment 1, wherein component A and B component used in combination according to the ratio of weight ratio 10: 1.
The bi-component polyurethane adhesive of above-mentioned resistance to acid liquid corrosion is applied in desulfuration chimney, acid solution treating pond field.
Claims (8)
1. a bi-component polyurethane adhesive for resistance to acid liquid corrosion, is characterized in that: mixed by component A and B component, is 0.8-20:1 according to weight ratio A:B;
Wherein said component A is composed of the following components by weight: polyether glycol 30-90, chainextender 1-20, acid resistance filler 10-50, softening agent 10-50, hydrolysis stabilizer 0.5-5, water-retaining agent 0.5-2, adhesion promoter 0.5-5, thixotropic agent 1-10, catalyzer 0.0l-0.2;
Described B component is that polyisocyanate resin 10-82 or described B component are composed of the following components by weight: polyisocyanate resin 10-80, softening agent 0.1-20;
Polyether glycol described in described component A comprises functionality and is 2-4 and molecular weight is the one in the polyoxypropylene polyol of 300-20000;
Described chainextender is di-alcohols;
Described acid resistance filler is silicon powder, mica powder or barium sulfate;
Described softening agent is phthalate;
Described hydrolysis stabilizer is Carbodiimides material;
Described adhesion promoter is silane coupling agent;
Described water-retaining agent is p-Methyl benzenesulfonyl isocyanate or oxazole alkanes moisture scavenger;
Described thixotropic agent is aerosil or organobentonite;
Described catalyzer is organic tin catalyzer;
Polyisocyanate resin described in described B component is polyisocyanates and derivative thereof; Described softening agent is phthalate.
2. the bi-component polyurethane adhesive of resistance to acid liquid corrosion as claimed in claim 1, is characterized in that: be 1-10:1 according to weight ratio A:B.
3. the bi-component polyurethane adhesive of resistance to acid liquid corrosion as claimed in claim 1, is characterized in that: described di-alcohols be a kind of in BDO, ethylene glycol, Diethylene Glycol, 1,6-hexylene glycol, HQEE or its arbitrarily between mixture;
Described phthalate is dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate or Di Iso Decyl Phthalate;
Described silane coupling agent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane;
Described organic tin catalyzer is dibutyl tin laurate, stannous octoate or dibutyltin mercaptide.
4. the bi-component polyurethane adhesive of resistance to acid liquid corrosion as claimed in claim 1, it is characterized in that: described polyisocyanates and derivative thereof are tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate, liquefied mdi, TDI tripolymer, HDI biuret or HDI tripolymer;
Described phthalate is dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate or Di Iso Decyl Phthalate.
5. the bi-component polyurethane adhesive of resistance to acid liquid corrosion as claimed in claim 1, is characterized in that: the granularity of silicon powder, mica powder or barium sulfate is 100 order-15000 orders.
6. the preparation method of the bi-component polyurethane adhesive of the resistance to acid liquid corrosion as described in one of claim 1 to 5, is characterized in that: prepare component A and B component respectively, wherein component A is prepared from by following steps:
A () at room temperature sequentially adds polyether glycol, chainextender, softening agent blended 10-90 minute under vacuum protection in stirring tank;
B () adds acid resistance filler, thixotropic agent, hydrolysis stabilizer, adhesion promoter, water-retaining agent, vacuum stirring 30 minutes;
C () adds catalyzer, vacuum stirring 10-90 minute;
(d) carry out degassed after, the component A product of paste can be obtained;
Be prepared from as follows when wherein B component is mixture:
(a) at room temperature in stirring tank order add polyisocyanate resin, softening agent, blended 15-60 minute under vacuum protection, obtain finely dispersed B component product;
Component A and B component are proportionally used in combination.
7. the preparation method of the bi-component polyurethane adhesive of resistance to acid liquid corrosion as claimed in claim 6, is characterized in that: the stirring tank of preparation component A is dual shaft planetary stirring tank, the enamel reaction stirring tank that preparation B component is.
8. the application of bi-component polyurethane adhesive in desulfuration chimney, acid solution treating pond field of the resistance to acid liquid corrosion that one of claim 1 to 5 is described.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210468595.4A CN103045153B (en) | 2012-11-20 | 2012-11-20 | Bi-component polyurethane adhesive of a kind of resistance to acid liquid corrosion and its preparation method and application |
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| CN201210468595.4A CN103045153B (en) | 2012-11-20 | 2012-11-20 | Bi-component polyurethane adhesive of a kind of resistance to acid liquid corrosion and its preparation method and application |
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| CN103045153B true CN103045153B (en) | 2015-11-25 |
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| CN103554410A (en) * | 2013-10-19 | 2014-02-05 | 泉州源利鞋材有限公司 | Shoe pad warm in winter and cool in summer as well as preparation method thereof |
| CN104559901B (en) * | 2014-12-26 | 2016-08-24 | 东莞市腾威电子材料技术有限公司 | A kind of two component adhesive and its preparation method and application |
| CN109206569B (en) * | 2017-07-03 | 2021-01-19 | 比亚迪股份有限公司 | Waterborne polyurethane, waterborne polyurethane adhesive and preparation method thereof |
| CN107652934A (en) * | 2017-09-30 | 2018-02-02 | 温州生物材料与工程研究所 | A kind of room temperature super fast curing double component solvent-free polyurethane structure glue and its preparation and application |
| CN111909348B (en) * | 2019-05-08 | 2022-10-28 | H.B.富乐公司 | Reactive polyurethane hot melt adhesive composition and preparation and application thereof |
| CN110343502A (en) * | 2019-06-13 | 2019-10-18 | 南京威邦新材料有限公司 | A kind of rubber-plastic composite floor board solvent-free polyurethane adhesive and preparation method thereof |
| CN112126400B (en) * | 2020-09-07 | 2022-08-12 | 深圳市安品有机硅材料有限公司 | Polyurethane corrosion-resistant material and preparation method thereof |
| CN115477913B (en) * | 2022-09-19 | 2023-08-18 | 华南理工大学 | Oil gel-based underwater adhesive material and preparation method and application thereof |
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| CN101037580A (en) * | 2007-04-30 | 2007-09-19 | 湖南神力实业有限公司 | Nano silicon micronization modified double components, solventless polyurethane adhesive and preparation method thereof |
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