CN109749595A - A kind of bi-component polyamides urea waterproof coating and preparation method thereof - Google Patents
A kind of bi-component polyamides urea waterproof coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of bi-component polyamides urea waterproof coatings and preparation method thereof, which includes: A and B component；In terms of mass fraction, the component A includes: 7-99 parts of polycarbodiimide, 3-20 parts of plasticizer and 0-20 parts of solvent；In terms of mass fraction, the B component includes: at least containing there are two 0-10 parts of 0-1 parts of 0-0.5 parts of 0-40 parts of 10-60 parts of 0-2 parts of 1-93 parts of polymer, pigment, filler, plasticizer, catalyst, dispersing agent, the solvent of acidic functionality and 0-5 parts of auxiliary agent.The present invention can effectively solve the problem that polyurethane water-proof paint preparation process, application, work progress to the tender subject of steam.
Description
Technical field
The invention belongs to water-repellent paint technical field, more particularly, to a kind of bi-component polyamides urea waterproof coating and its
Preparation method.
Background technique
Bicomponent polyurethane coating has been used widely in each industrial circle at present, including: auto industry,
Automobile repairing paint, coil coating, highway, bridge, chemical industry equipment etc..Compared to one-can urethane coating, having can low temperature
Solidification, not vulnerable to outstanding features such as ambient temperature and humidity influences.Common bicomponent polyurethane coating system is that hydroxy polybasic is pure and mild
Polyisocyanate curing agent system.Curing agent component is made of aromatic series or aliphatic polyisocyante or its prepolymer；It is polynary
Alkoxide component is by epoxy resin, hydroxyl alkyd resins, organic hydroxy silicate resin, hydroxy polyester resin, hydroxy chloride wax tree rouge, hydroxyl third
Olefin(e) acid resin and above two or two or more resins, add various inorganic fillers, such as: calcium carbonate, mica, talcum
Powder, kaolin etc., organic pigment, various auxiliary agents etc..With excellent adhesive force, chemical-resistant, quick-drying etc..Bi-component is poly-
Urethane is with the obvious advantage in coating allocation process.Polyol moiety can be adjusted arbitrarily, and curing agent part also has multiple kinds can
It is selective.The designability of curing agent part is also higher, can be isocyanate-monomer, or isocyanate-monomer from it is different
The isocyanate prepolymer of structure, the polyethers of molecular weight or polyester polyol reaction.Contained according to the isocyanates of curing agent component
The hydroxy radical content of amount and polyol component determines the mixing ratio of two components.But the isocyanate groups in polyurethane curing agent
Reactivity is high, is also easy to produce bubble to water vapor sensitive and there is a problem of that free isocyanate monomer residual toxicity is big.
Although polyol component is free of isocyanate groups, in process of production, it is still desirable to dehydration.It avoids
Moisture content is excessively high (no more than 0.05%) in system, and after otherwise mixing with curing agent, the hydroxyl of moisture and polyalcohol occurs
Competitive reaction causes stoichiometric ratio unbalance, while the carbon dioxide that side reaction is released has unfavorable shadow to film performance and appearance
It rings.Process aspect need to dry inorganic powder, and after then mixing with liquid materials components such as polyalcohols, 110-120 DEG C of vacuum is stirred
Dehydration is mixed, until the moisture content measured is no more than 0.05%.
Bicomponent polyurethane coating includes isocyanate curing agent, polyol component.Complex process in dope preparing process:
Polyol component preparation process needs to carry out hard vacuum, high temperature dehydration, controls moisture content, reduces trace water and isocyano
Competitive reaction, this process consumes a large amount of electric energy；Isocyanate curing agent component needs to control free isocyanate content,
Volatilizable content of monomer is reduced, to protect the health of construction personnel and owner.Meanwhile condition of storage requires strictly, to avoid
The contact of moisture is opened bucket and is used.
Summary of the invention
The object of the present invention is to provide a kind of bi-component polyamides urea waterproof coatings and preparation method thereof, solid to solve polyurethane
Isocyanate groups reactivity in agent is high, is also easy to produce bubble to water vapor sensitive and free isocyanate monomer remains poison
The problems such as property is big, and curing agent and polyol component are both needed to high temperature, vacuum dehydration, and energy consumption is high.
To achieve the goals above, one aspect of the present invention provides a kind of bi-component polyamides urea waterproof coating, the water-repellent paint
It include: A and B component；
In terms of mass fraction, the component A includes: 7-99 parts of polycarbodiimide, 3-20 parts of plasticizer and solvent 0-20
Part；
In terms of mass fraction, the B component includes: at least containing there are two 1-93 parts of polymer, the pigment of acidic functionality
0-2 parts, 10-60 parts of filler, 0-40 parts of plasticizer, 0-0.5 parts of catalyst, 0-1 parts of dispersing agent, 0-10 parts of solvent and auxiliary agent 0-5
Part.
Another aspect of the present invention provides a kind of preparation method of above-mentioned bi-component polyamides urea waterproof coating, the preparation method
Include:
The preparation of component A: by polycarbodiimide, plasticizer and optional solvent are uniformly mixed, and vacuum outgas obtains institute
State component A；
The preparation of B component: (1) by the polymer and optional plasticizer and dispersing agent at least containing two acidic functionalities
It is uniformly mixed, heating is added filler and optional pigment, vacuum outgas, obtains the B component；
At least one of catalyst, solvent and auxiliary agent are uniformly mixed by optional cooling with the mixture of step (1),
Vacuum outgas obtains the B component.
Technical solution of the present invention has the following beneficial effects:
(1) present invention can effectively solve the problem that polyurethane water-proof paint preparation process, application, work progress to water vapor sensitive,
The problem of being also easy to produce bubble；
(2) present invention, which is able to solve polyurethane water-proof paint product, has the harm of free isocyanate, such as
Requirement of Shenzhen terrestrial reference to free TDI；
(3) present invention is not necessarily to the complexity such as high temperature dehydration when preparing water-repellent paint using polycarbodiimide as curing agent
Technique, can effectively shorten the production time and reduce the energy use.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.Phase
Instead, these embodiments are provided so that the present invention is more thorough and complete, and can be by the scope of the present invention completely
It is communicated to those skilled in the art.
An aspect of of the present present invention provides a kind of bi-component polyamides urea waterproof coating, which includes: A and B component；
In terms of mass fraction, the component A includes: 7-99 parts of polycarbodiimide, 3-20 parts of plasticizer and solvent 0-20
Part；
In terms of mass fraction, the B component includes: at least containing there are two 1-93 parts of polymer, the pigment of acidic functionality
0-2 parts, 10-60 parts of filler, 0-40 parts of plasticizer, 0-0.5 parts of catalyst, 0-1 parts of dispersing agent, 0-10 parts of solvent and auxiliary agent 0-5
Part.
The present invention mainly passes through polymer of the polycarbodiimide as curing agent and the acidic functionality at least containing there are two
Reaction generates polyamides urea, and film-forming obtains polyamides urea waterproof coating, to solve to be met in polyurethane water-proof paint preparation process
To curing agent to water vapor sensitive, be also easy to produce bubble, remain free isocyanate curing agent in product the problems such as.
In accordance with the present invention it is preferred that the polycarbodiimide is derived from isocyanates, oligomeric isocyanates, isocyanide
At least one of addition product and isocyanates and the addition product of polyamine of acid esters and polyalcohol；
The isocyanates is aliphatic isocyanates and/or aromatic isocyanate；
The aliphatic isocyanates be preferably selected from isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate,
At least one of trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate；
It is sub- that the aromatic isocyanate is preferably selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene two
At least one of methyl diisocyanate and tetramethyl xylylene diisocyanate；
Wherein, the polycarbodiimide is preferably derived from toluene di-isocyanate(TDI) and/or diphenylmethane diisocyanate
Ester.
In the present invention, the degree of functionality of the polycarbodiimide is greater than or equal to 2.
In the present invention, the preparation method of polycarbodiimide is the customary preparation methods of this field；Polycarbodiimide can
With self-control or it is commercially available.
In the present invention, the oligomeric isocyanates are preferably uretdione and/tripolymer.
In accordance with the present invention it is preferred that the weight average molecular weight of the polycarbodiimide is 500-3000；Further preferably
500-2000。
In accordance with the present invention it is preferred that the acidic functionality at least containing the polymer there are two acidic functionality is selected from
At least one of carboxylic acid group, carbonyldioxy, sulfonic group, mercapto, phenolic group, phosphate and sulfinic acid base；
It is described to be at least preferably unsaturated fat acid polymer, at least contain two containing the polymer there are two acidic functionality
At least one of polyester and acrylate copolymer of a acidic functionality, further preferably dimer (fatty acid) yl, trimerization fat
At least one of acid and carboxyl acrylic resin.
The unsaturated fat acid polymer is preferably C10-C50Unsaturated fat acid polymer；Further preferably C18
Unsaturated fat acid polymer and/or C16Unsaturated fat acid polymer.
In accordance with the present invention it is preferred that the weight average molecular weight at least containing the polymer there are two acidic functionality is
100-3500；Further preferably 100-1500.
In accordance with the present invention it is preferred that the catalyst is organo-metallic catalyst；Preferably organozinc catalyst, organic
At least one of bismuth catalyst and organotin catalysts；Further preferably dibutyl tin dilaurate；The tin dilaurate
Dibutyl tin is preferably the T-12 of air chemical products Co., Ltd.
The plasticizer is preferably selected from chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, O-phthalic
Sour dinonyl, citric acid ester plasticizer, at least one of vegetable oil ester plasticizer and polyether polyol；It is further excellent
It is selected as diisononyl phthalate and/or polyether polyol；
The compatibility of plasticizer of the invention and polyamides base urea elastomers is good, due to plasticizer and polyamides base urea elastomers
Compatibility is good, and plasticizer will not migrate in long-term use, and stability and concertedness are significant.
The filler is preferably selected from kaolin, cement, coarse whiting, barium sulfate, magnesia, calcium oxide, wollastonite, silicon powder,
At least one of talcum powder and mica powder；Further preferably coarse whiting and/or mica powder.
In accordance with the present invention it is preferred that the pigment is selected from carbon black, at least one of titanium dioxide and iron oxide yellow；
The solvent be organic solvent, the organic solvent be selected from toluene, dimethylbenzene, 120# solvent naphtha, 150# solvent naphtha,
Ethyl acetate, butyl acetate, at least one of n,N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).Preferably
Butyl acetate.
In accordance with the present invention it is preferred that the auxiliary agent includes 0-1 parts of defoaming agent in terms of mass fraction, 0-1 parts of levelling agent and
0-1 parts of rheological agent.
Another aspect of the present invention provides the preparation method of above-mentioned bi-component polyamides urea waterproof coating, the preparation method packet
It includes:
The preparation of component A: by polycarbodiimide, plasticizer and optional solvent are uniformly mixed, and vacuum outgas obtains institute
State component A；
The preparation of B component: (1) by the polymer and optional plasticizer and dispersing agent at least containing two acidic functionalities
It is uniformly mixed, heating is added filler and optional pigment, vacuum outgas, obtains the B component；
At least one of catalyst, solvent and auxiliary agent are uniformly mixed by optional cooling with the mixture of step (1),
Vacuum outgas obtains the B component.
In accordance with the present invention it is preferred that being warming up to 60-70 DEG C in the preparation of B component；It is cooled to 45-55 DEG C.
Preferably, in application, with B component being 1:(1-5 with weight ratio by component A) mix, then film,
Maintenance.
Bi-component polyamides urea waterproof coating of the invention, compared with traditional polyurethane two-component water-repellent paint, production and
Construction technology is simple, and no free isocyanate residual, raw material are without stringent dehydration.Storage stability is good, production process energy conservation
Environmental protection.Occasion suitable for the application of all Two-component Waterproof Polyurethane Coatings.
The present invention is further illustrated by the following examples:
Dibutyl tin dilaurate used in following embodiment is purchased from the T-12 of air chemical products Co., Ltd；It is used
Dimer (fatty acid) yl is purchased from company, Anqing Hong Yu Chemical Co., Ltd., trade mark HY-005；Trimerized fatty acids used are purchased from Liancheng hundred
New science and technology Co., Ltd, trade mark BX-6；Polyether polyol used is purchased from the 330N of Shanghai Gaoqiao petro-chemical corporation；Dispersing agent purchase used
From the Disperbyk-108 of BYK company；Carboxyl acrylic resin used is purchased from Zibo Ze Yang Chemical Co., Ltd., and the trade mark is
ZY01。
Embodiment 1
The preparation of component A: 11 parts of polycarbodiimide are weighed by mass fraction, plasticizer phthalic acid dinonyl 2
Part, it 16 parts of chlorinated paraffin, stirs evenly, vacuum outgas, discharges spare.
The preparation of B component: 9 parts of dimer (fatty acid) yl are weighed by mass fraction, is stirred using intense stirring device, and be warming up to
65 DEG C, sequentially add 6 parts of mica powders, 25 parts of coarse whitings, vacuum outgas；50 DEG C are cooled to, is added 1 part of butyl acetate, defoaming agent
0.1 part of BYK-054, vacuum outgas is spare.
Wherein, by toluene di-isocyanate(TDI), the condensation reaction under the catalysis of organic phosphine is made the polycarbodiimide, and
It is blocked with single cyanate；The weight average molecular weight of the polycarbodiimide is 900.The weight average molecular weight of the dimer (fatty acid) yl is
560；
In application, A:B is stirred evenly by weight 1:1, then film, maintenance.
Embodiment 2
The preparation of component A: 18 parts of polycarbodiimide are weighed by mass fraction, plasticizer phthalic acid dinonyl 1
Part, it 2 parts of butyl acetate, 5 parts of chlorinated paraffin, stirs evenly, vacuum outgas, discharges spare.
The preparation of B component: weighing 9 parts of dimer (fatty acid) yl by mass fraction, and 2 parts of trimerized fatty acids, 18.5 parts of chlorinated paraffin,
0.3 part of dispersing agent Disperbyk-108 is stirred using intense stirring device, and is warming up to 65 DEG C, and 7 parts of mica powders are sequentially added,
36.5 parts of coarse whitings, vacuum outgas；50 DEG C are cooled to, is added 5 parts of solvent acetic acid butyl ester, 0.2 part of defoaming agent BYK-054, vacuum is de-
Gas, it is spare.
Wherein, the polycarbodiimide by methyl diphenylene diisocyanate the condensation reaction system under the catalysis of organic phosphine
At, and blocked with single cyanate；The weight average molecular weight of the polycarbodiimide is dividing equally again for 1360 dimer (fatty acid) yls
Son amount is 560, and the weight average molecular weight of the trimerized fatty acids is 900；
In application, A:B is stirred evenly by weight 1:3, then film, maintenance.
Embodiment 3
The preparation of component A: 13 parts of polycarbodiimide are weighed by mass fraction, plasticizer phthalic acid dinonyl 3
Part, it 1 part of butyl acetate, 3 parts of chlorinated paraffin, stirs evenly, vacuum outgas, discharges spare.
The preparation of B component: 9 parts of dimer (fatty acid) yl are weighed by mass fraction, 3 parts of polyether polyol, 6 parts of chlorinated paraffin, is adopted
It is stirred with intense stirring device, and is warming up to 65 DEG C, sequentially add 2 parts of mica powders, 20 parts of coarse whitings, vacuum outgas；It is cooled to 50
DEG C, it is added 0.01 part of catalyst dibutyltin dilaurylate, vacuum outgas is spare.
Wherein, by toluene di-isocyanate(TDI), the condensation reaction under the catalysis of organic phosphine is made the polycarbodiimide, and
It is blocked with single cyanate；The weight average molecular weight of the polycarbodiimide is 900.The weight average molecular weight of the dimer (fatty acid) yl is
560
In application, A:B is stirred evenly by weight 1:2, then film, maintenance.
Embodiment 4
The preparation of component A: 90 parts of polycarbodiimide are weighed by mass fraction, plasticizer phthalic acid dinonyl 3
Part, it 10 parts of butyl acetate, 3 parts of chlorinated paraffin, stirs evenly, vacuum outgas, discharges spare.
The preparation of B component: 60 parts of carboxyl acrylic resin (weight average molecular weight 800) is weighed by mass fraction, polyethers is more
3 parts of first alcohol, 6 parts of chlorinated paraffin, 10 parts of n,N-Dimethylformamide (DMF) is stirred, and be warming up to 65 using intense stirring device
DEG C, sequentially add 2 parts of mica powders, 20 parts of coarse whitings, vacuum outgas；50 DEG C are cooled to, catalyst dibutyltin dilaurylate is added
0.03 part, 0.3 part of levelling agent, 0.3 part of rheological agent, vacuum outgas is spare.
Wherein, by toluene di-isocyanate(TDI), the condensation reaction under the catalysis of organic phosphine is made the polycarbodiimide, and
It is blocked with single cyanate；The weight average molecular weight of the polycarbodiimide is 900；The levelling agent is BYK306, and rheological agent is
BYK410
In application, A:B is stirred evenly by weight 1:2, then film, maintenance.
Test case
According to GB/T19250-2013 standard, the water-repellent paint of embodiment preparation is tested for the property, concrete outcome is shown in
Table 1.
Table 1
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of bi-component polyamides urea waterproof coating, which is characterized in that the water-repellent paint includes: A and B component；
In terms of mass fraction, the component A includes: 7-99 parts of polycarbodiimide, 3-20 parts of plasticizer and 0-20 parts of solvent；
In terms of mass fraction, the B component includes: at least containing there are two 1-93 parts of polymer, the pigment 0-2 of acidic functionality
Part, 10-60 parts of filler, 0-40 parts of plasticizer, 0-0.5 parts of catalyst, 0-1 parts of dispersing agent, 0-10 parts of solvent and 0-5 parts of auxiliary agent.
2. bi-component polyamides urea waterproof coating according to claim 1, wherein the polycarbodiimide is derived from isocyanide
Acid esters, oligomeric isocyanates, the addition product and isocyanates of isocyanates and polyalcohol and polyamine addition product in extremely
Few one kind；
The isocyanates is aliphatic isocyanates and/or aromatic isocyanate；
The aliphatic isocyanates are preferably selected from isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, front three
At least one of base hexamethylene diisocyanate and hexamethylene diisocyanate；
The aromatic isocyanate is preferably selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne
At least one of diisocyanate and tetramethyl xylylene diisocyanate；
Wherein, the polycarbodiimide is preferably derived from toluene di-isocyanate(TDI) and/or methyl diphenylene diisocyanate.
3. bi-component polyamides urea waterproof coating according to claim 1, wherein the Weight-average molecular of the polycarbodiimide
Amount is 500-3000.
4. bi-component polyamides urea waterproof coating according to claim 1, wherein described at least containing there are two acidic functionalities
Polymer acidic functionality in carboxylic acid group, carbonyldioxy, sulfonic group, mercapto, phenolic group, phosphate and sulfinic acid base
It is at least one；
Described is preferably at least unsaturated fat acid polymer, at least containing there are two acid containing the polymer there are two acidic functionality
At least one of polyester and acrylate copolymer of property functional group, further preferably dimer (fatty acid) yl, trimerized fatty acids and
At least one of carboxyl acrylic resin.
5. bi-component polyamides urea waterproof coating according to claim 1, wherein described at least containing there are two acidic functionalities
Polymer weight average molecular weight be 100-3500.
6. bi-component polyamides urea waterproof coating according to claim 1, wherein the catalyst is metal organic catalysis
Agent；Preferably at least one of organozinc catalyst, organic bismuth catalyst and organotin catalysts；Further preferably February
Dilaurylate；
The plasticizer is preferably selected from chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, phthalic acid two
Different nonyl ester, citric acid ester plasticizer, at least one of vegetable oil ester plasticizer and polyether polyol；Further preferably
Diisononyl phthalate and/or polyether polyol；
The filler is preferably selected from kaolin, cement, coarse whiting, barium sulfate, magnesia, calcium oxide, wollastonite, silicon powder, talcum
At least one of powder and mica powder；Further preferably coarse whiting and/or mica powder.
7. bi-component polyamides urea waterproof coating according to claim 1, wherein the pigment be selected from carbon black, titanium dioxide and
At least one of iron oxide yellow；
The solvent is organic solvent, and the organic solvent is selected from toluene, dimethylbenzene, 120# solvent naphtha, 150# solvent naphtha, acetic acid
Ethyl ester, butyl acetate, at least one of n,N-Dimethylformamide and dimethyl sulfoxide.
8. bi-component polyamides urea waterproof coating according to claim 1, wherein in terms of mass fraction, the auxiliary agent includes
0-1 parts of defoaming agent, 0-1 parts and rheological agent 0-1 parts of levelling agent.
9. the preparation method of bi-component polyamides urea waterproof coating described in any one of claim 1-8, which is characterized in that should
Preparation method includes:
The preparation of component A: by polycarbodiimide, plasticizer and optional solvent are uniformly mixed, and vacuum outgas obtains the A
Component；
The preparation of B component: (1) by the polymer and optional plasticizer and dispersant at least containing two acidic functionalities
Uniformly, it heats up, filler and optional pigment, vacuum outgas is added, obtains the B component；
At least one of catalyst, solvent and auxiliary agent are uniformly mixed, vacuum by optional cooling with the mixture of step (1)
Degassing, obtains the B component.
10. preparation method according to claim 9, wherein in the preparation of B component, be warming up to 60-70 DEG C；It is cooled to 45-
55℃。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786657A (en) * | 1987-07-02 | 1988-11-22 | Minnesota Mining And Manufacturing Company | Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate |
| CN108137951A (en) * | 2015-07-31 | 2018-06-08 | 巴斯夫欧洲公司 | It is used to form the paint base composition of the coloring of N- acylureas coatings |
-
2018
- 2018-12-29 CN CN201811636728.8A patent/CN109749595A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786657A (en) * | 1987-07-02 | 1988-11-22 | Minnesota Mining And Manufacturing Company | Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate |
| CN108137951A (en) * | 2015-07-31 | 2018-06-08 | 巴斯夫欧洲公司 | It is used to form the paint base composition of the coloring of N- acylureas coatings |
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