CN117625022A - Interpenetrating polymer network IPN-based two-component asparagus coating and application thereof - Google Patents
Interpenetrating polymer network IPN-based two-component asparagus coating and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 94
- 239000011248 coating agent Substances 0.000 title claims abstract description 87
- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 235000005340 Asparagus officinalis Nutrition 0.000 title claims abstract description 29
- 244000003416 Asparagus officinalis Species 0.000 title 1
- 229920002396 Polyurea Polymers 0.000 claims abstract description 93
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- -1 polyoxypropylene Polymers 0.000 claims abstract description 40
- 150000002148 esters Chemical class 0.000 claims abstract description 36
- 241000234427 Asparagus Species 0.000 claims abstract description 28
- 229920000608 Polyaspartic Polymers 0.000 claims abstract description 19
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 4
- 108010064470 polyaspartate Proteins 0.000 claims description 40
- 239000012948 isocyanate Substances 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 23
- 150000002513 isocyanates Chemical class 0.000 claims description 22
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 20
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 241000183024 Populus tremula Species 0.000 claims description 4
- 230000003712 anti-aging effect Effects 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical group C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000013638 trimer Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 229920002994 synthetic fiber Polymers 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 229920006243 acrylic copolymer Polymers 0.000 abstract description 2
- 125000002723 alicyclic group Chemical group 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000009472 formulation Methods 0.000 description 24
- 229920002943 EPDM rubber Polymers 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
- 239000004743 Polypropylene Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000003085 diluting agent Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000004567 concrete Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000013022 formulation composition Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to an asparagus polyurea coating, in particular to a double-component asparagus polyurea coating based on an Interpenetrating Polymer Network (IPN) and application thereof; the polyurea modified polyaspartic ester resin provided by the invention improves the flexibility and the reactivity of the traditional alicyclic polyaspartic ester resin, so that the polyurea modified polyaspartic ester resin can provide better flexibility and adhesion when being used as a surface coating of a low-surface-energy synthetic material. Meanwhile, the polyoxypropylene ether segment in the polyurea structure can generate good compatibility with acrylate hydroxyalkyl ester, so that the compatibility between a first polymer phase (aliphatic polyurea phase) and a second polymer phase (acrylic copolymer phase) in the interpenetrating polymer network is increased. Thereby, the excellent aging resistance, impact resistance and low temperature flexibility of the polyurea polymer and the excellent adhesive property of the polyacrylate copolymer are exerted to the maximum extent.
Description
Technical Field
The invention relates to an asparagus polyurea coating, in particular to a double-component asparagus polyurea coating based on an Interpenetrating Polymer Network (IPN) and application thereof
Background
The aliphatic asparagus polyurea coating is a novel polyurea coating, and has the characteristics of outstanding ageing resistance, corrosion resistance, high gloss, high toughness, quick solidification, easy construction and the like due to the fact that a main chain of the aliphatic asparagus polyurea coating is provided with a hindered amine structure and a secondary amino active group, so that the aliphatic asparagus polyurea coating is more suitable for being applied to the industrial field than the traditional aromatic polyurea coating. In recent years, the product forms of the asparagus polyurea coating comprise solvent systems, high-solid-content systems, solvent-free systems and aqueous systems, and the application range of the asparagus polyurea coating relates to the fields of railway vehicles, rail transit, bridge steel structures, automobile manufacturing and repairing, engineering machinery, containers, mining machinery, woodware and the like. Nevertheless, the drawbacks of the asparaguse polyurea coating are evident, i.e. its adhesion to the base (including metal, rubber and plastic, etc.) is significantly lower than with conventional coatings of acrylic and epoxy, etc. The main reasons for this are the high surface tension and the high curing speed of the coating due to the strong polarity and high reactivity of the amino groups, which affect the adhesion properties of the coating film to the substrate.
The defect of the adhesive force of the asparagus polyurea coating severely restricts the application of the asparagus polyurea coating to special occasions, particularly low-surface-energy materials. For example, high speed motor car Ethylene Propylene Diene Monomer (EPDM) windshield rubber and automotive polypropylene (PP) bumpers are required to be protected with a special coating having high performance such as high aging resistance, high corrosion resistance, high flexibility and high impact resistance, which are particularly compatible with the inherent properties of the asparaguse coating. But the EPDM and PP materials are low surface energy materials, and in the traditional coating process, a primer (PP water) capable of improving the adhesive force must be coated first, and then the middle coating and the top coating are applied. Although the performance of the asparagus polyurea coating can integrate the middle coating and the top coating in the traditional process, the adhesion of the asparagus polyurea coating can be ensured by means of a PP water primer.
Disclosure of Invention
Object of the Invention
The invention provides a double-component asparaurea coating based on an Interpenetrating Polymer Network (IPN) aiming at low-surface-energy synthetic materials such as EPDM and PP, so that the coating can be directly coated on low-surface-energy base materials such as EPDM, PP and the like without using PP water priming paint. Meanwhile, the traditional two-way coating (middle coating and top coating) process can be simplified into a single-way coating (top coating) process.
Technical proposal
The invention firstly relates to a double-component asparagus polyurea coating based on an Interpenetrating Polymer Network (IPN); the invention also relates to a preparation method of the double-component asparagus polyurea coating based on the interpenetrating polymer network IPN; the invention further relates to a use method of the two-component asparaguses polyurea coating based on the interpenetrating polymer network IPN on the base surface of the low-surface-energy synthetic material.
The invention relates to a double-component aspen polyurea coating based on an Interpenetrating Polymer Network (IPN), which is characterized in that an aliphatic polyurea cross-linked polymer is used for forming a first polymer of the IPN, and a polyacrylate copolymer is used for forming a second polymer of the IPN.
Wherein the aliphatic polyurea cross-link constituting the first polymer of the IPN is formed by:
1 polyurea modified polyaspartic esters
2 polyaspartic acid ester
3 isocyanate curing agent
Crosslinking to obtain the final product.
Wherein the polyurea modified polyaspartate has the following structure (formula 1):
wherein R1 is a C1-C6 aliphatic chain alkylene, an alicyclic alkylene, or a combination thereof; r2 is an alkylene group of isophorone diisocyanate (IPDI), 6 methylene diisocyanate (HDI) or Hydrogenated MDI (HMDI), R4 is a C10-C30 linear alkylene group; r3 and R5 are hydrogen or C1-C8 alkyl or ester groups, which may be the same or different.
Wherein said polyacrylate copolymer comprising the IPN second polymer is formed from:
1 diacetone acrylamide DAAM,
2. hydroxy alkyl acrylate
3. Acrylic acid alkyl ester
4. Organoboron amine complex initiators
And (3) copolymerizing.
The invention also relates to a preparation method of the double-component asparagus polyurea coating based on the interpenetrating polymer network IPN, which is characterized in that the component A (resin component) is composed of:
1 polyurea modified polyaspartic esters
2 polyaspartic acid ester
3 diacetone acrylamide DAAM
4. Hydroxy alkyl acrylate
5. Acrylic acid alkyl ester
6. Organoboron amine complex initiators
7. Each coating auxiliary agent
8. Suitable diluents
Is composed of the components.
The component B (curing agent component) is composed of:
1. isocyanate prepolymers
2 isophorone diisocyanate (IPDI)
Is composed of the components.
In the component A of the double-component asparate polyurea coating based on the interpenetrating polymer network IPN, the preparation of the polyurea modified polyaspartate is characterized by a two-step process, wherein the first step is to condense a difunctional amino compound and a difunctional aliphatic isocyanate to obtain an isocyanate-terminated polyurea prepolymer. And secondly, condensing the isocyanate-terminated polyurea prepolymer obtained in the first step with polyaspartic acid ester resin to obtain the polyurea modified polyaspartic acid ester.
In the first step, the difunctional amino compound may be a primary amino-terminated amine-terminated polyether (e.g., jeffamine D series) or a secondary amino-terminated amine-terminated polyether (e.g., jeffamine SD series), including but not limited to an amine-terminated polyether having a molecular weight of 200 to 3000, with a secondary amino compound having a molecular weight of 400 to 1000 being preferred.
The difunctional aliphatic isocyanates include, but are not limited to, isophorone diisocyanate (IPDI), 6 methylene diisocyanate (HDI), hydrogenated MDI (HMDI), xylylene Diisocyanate (XDI), with IPDI and HMDI being preferred.
The equivalent ratio [ NCO ]/[ N ] of the aliphatic isocyanate to the synthesis of the difunctional amino compound is 2.05:1, preferably 2.0:1.
The condensation reaction of the difunctional amino compound and the aliphatic isocyanate can be carried out according to a synthesis method commonly used in the technical field of the existing polyurethane, for example, the difunctional amino compound is firstly slowly dripped into the aliphatic isocyanate at the temperature of 10-20 ℃, the temperature is kept for reaction for 1-2 hours, then the temperature is increased to 55-60 ℃ for continuous reaction until the NCO% value reaches a theoretical design value, and thus the isocyanate-terminated polyurea prepolymer is obtained.
In the second step, the polyaspartic acid ester resin which performs condensation reaction with the isocyanate-terminated polyurea prepolymer obtained in the first step comprises, but is not limited to, polyaspartic acid ester products commonly used in the technical field of asparate polyurea, such as Desmophen NH1420, NH1520 and other specifications of Korsche, and can also be synthesized by a Michael addition process by using proper polyamine and proper unsaturated compound, such as a method reported in Chinese patent ZL 201910161998.6.
The equivalent ratio [ NCO ]/[ N ] of the isocyanate-terminated polyurea prepolymer obtained in the first step to the synthesis of the polyaspartic acid ester resin is 1:1.05, preferably 1:1.
In the following description, unless otherwise specified, the amounts or percentages of the components, ingredients, and so forth are in parts by weight.
The reaction of the isocyanate-terminated polyurea prepolymer with the polyaspartic acid ester resin in the second step can be carried out without adding a catalyst or with adding a proper catalyst to accelerate the reaction speed. Suitable catalysts include, but are not limited to, stannous octoate, dibutyl tin dilaurate, zinc neodecanoate, and the like. The addition amount is 0.02 to 0.1%, preferably 0.05% of the total reaction components.
The reaction of the isocyanate-terminated polyurea prepolymer precursor with the polyaspartic acid ester resin in the second step may be carried out without adding a diluent or with the addition of a suitable diluent to adjust the viscosity. Suitable diluents include, but are not limited to, toluene, xylene, tetrahydrofuran, butyl acetate, and the like. The addition amount is 5 to 30%, preferably 10 to 20% of the total reaction components.
The condensation reaction of the isocyanate-terminated polyurea prepolymer with the polyaspartate resin in the second step can be carried out according to the synthesis method commonly used in the technical field of the existing polyurethane, for example, the isocyanate-terminated polyurea prepolymer and the polyaspartate resin are directly mixed in a reactor, a solvent and a catalyst are added if necessary, and the mixture is reacted for 10 to 12 hours at a temperature of 40 to 60 ℃ until the NCO% value is zero or until 2270 in an infrared spectrogram -1 The nearby peak disappeared. Thereby obtaining polyurea modified polyaspartic esters.
In the component A of the double-component aspartyl polyurea coating based on the interpenetrating polymer network IPN, the use proportion of the polyurea modified polyaspartate can be 10-40%, preferably 20-30% of each polymer monomer in the component A.
In the component A of the interpenetrating polymer network IPN-based two-component asparate polyurea coating, the polyaspartate resin comprises, but is not limited to, polyaspartate products commonly used in the technical field of asparate polyurea, such as Desmophen NH1420, NH1520, NH1220 and other specifications, and can also be synthesized by a Michael addition process by selecting proper polyamine and proper unsaturated compounds, such as a method reported in China patent ZL 201910161998.6. They can be used alone or in combination according to the desired properties.
In the component A of the dual-component asparate polyurea coating based on the interpenetrating polymer network IPN, the polyaspartate resin can be used in a proportion of 10-40%, preferably 20-30%, of each polymer monomer in the component A.
The polyacrylate copolymer constituting the second polymer of the IPN is diacetone acrylamide (DAAM) and may be used in a proportion of 10 to 30%, preferably 15 to 20%, of the monomers of the respective polymers of the a component.
In the component A of the double-component asparagus coating based on the interpenetrating polymer network IPN, the hydroxyl alkyl acrylate can be hydroxyethyl acrylate, hydroxypropyl acrylate and preferably hydroxyethyl acrylate. The proportion of the polymer monomer in the component A may be 5 to 20%, preferably 5 to 10%.
In the component A of the two-component asparagus coating based on the interpenetrating polymer network IPN, the alkyl acrylate can be methyl acrylate or ethyl acrylate, and preferably methyl acrylate or not. The amount of the polymer may be 0 to 10%, preferably 0 to 5% of the amount of each polymer monomer in the component A.
In the component A of the interpenetrating polymer network IPN-based two-component asparaguse polyurea coating, the organic boron amine complex is a latent initiator and is a complex of alkyl boron and diamine. The structural formula is shown as follows (formula 2):
wherein R is 1 、R 2 、R 3 Are C1-C10 alkyl groups, which may be the same or different. Am is a primary dibasic amine. The V value is the ratio of nitrogen atoms to boron atoms in the formula.
The primary diamines include, but are not limited to, ethylenediamine, hexamethylenediamine or amine-terminated ethers having a molecular weight of 200 to 400, preferably amine-terminated polyethers having a molecular weight of 400 are used.
The molar ratio of the organoborane to the diamine addition complex is determined by a V value, namely the ratio of nitrogen atoms to boron atoms in the complex is determined to be in an effective range, and the effective ratio is 1-4:1, preferably 1:1.
The organoboranes include, but are not limited to, triphenylborane, triethylborane, tri-n-propylborane, tri-n-butylborane, preferably tri-n-butylborane.
The amount of the organoborane and diamine addition complex initiator can be such that the boron content in the complex is 0.05-0.8%, preferably 0.1-0.3% of the total amount of each unsaturated polymeric monomer in the component A.
The preparation of organoborane amine complexes can be carried out by reference to the relevant literature (H.C.Brown A Convenent, highly Efficient Synthesis of Triorganylboranes via a Modified Organometallic Route, J.org.chem.1986, vol.51, 527-432).
In the component A of the interpenetrating polymer network IPN-based double-component asparaguse polyurea coating, each coating auxiliary agent comprises but is not limited to a leveling agent, a defoaming agent, a wetting agent, a dispersing agent, an antioxidant, an anti-aging agent, a pigment, a filler and the like, and each addition amount can be executed according to the suggestion of a relevant provider or can be used according to the technical experience and habit of the current coating technical field.
In the component A of the interpenetrating polymer network IPN-based two-component asparaguse coating, the used diluents include, but are not limited to, toluene, xylene, tetrahydrofuran, butyl acetate and the like. The addition amount is 0-20%, preferably 5-15% of the total amount of component A.
The preparation method of the component A of the double-component asparaguse coating based on the interpenetrating polymer network IPN can be carried out according to the following sequence:
1, firstly, uniformly stirring and mixing polyurea modified polyaspartic acid ester, polyaspartic acid ester resin, hydroxyl alkyl acrylate and alkyl acrylate according to a proportion.
2 a calculated amount of diacetone acrylamide (DAAM) powder was added to the above mixture and stirred well until the powder was completely dissolved.
3, weighing the calculated amount of organoboron amine complex initiator, then adding the initiator into the mixed solution, and uniformly stirring.
And 4, adding assistants such as color paste, flatting agent, defoamer, wetting agent, dispersing agent, antioxidant, anti-aging agent and the like into the mixed solution in turn according to the requirement of a paint formula, and then stirring and dispersing for 30min at a high speed (2000 rpm).
And 5, adding a proper amount of solvent according to construction requirements to adjust viscosity, and stirring uniformly to obtain the component A.
The component B comprises: the isocyanate prepolymer is synthesized by compounding isocyanate and polymeric dihydric alcohol, wherein the compound isocyanate is formed by mixing 55-65% (weight percent) of HDI trimer and 35-45% (weight percent) of IPDI, HDI or XDI.
The polymeric glycol may be a polyether glycol including, but not limited to, polyoxypropylene glycol, ethylene oxide glycol, polytetrahydrofuran glycol, and the like. They have a molecular weight of from 1000 to 3000, preferably 2000. As the polyether glycol component, various components may be used alone or after being mixed in any ratio.
The polymeric glycol may also be a polyester glycol including, but not limited to, a polyadipate glycol, a polycaprolactone glycol, and a polycarbonate glycol. They have a molecular weight of from 1000 to 3000, preferably 2000. As the polyester diol component, various ones may be used alone or after being mixed in any ratio.
When the isocyanate prepolymer is synthesized, the equivalent ratio [ NCO ]/[ OH ] of the total amount of NCO of the composite isocyanate to the total amount of OH of the polymeric dihydric alcohol is 3.0-6.0:1, preferably 4.0-5.0:1.
The synthesis of the isocyanate prepolymer can be carried out without adding a catalyst, and a proper catalyst can be added to accelerate the reaction speed. Suitable catalysts include, but are not limited to, stannous octoate, dibutyl tin dilaurate, zinc neodecanoate, and the like. The addition amount is 0.02 to 0.1%, preferably 0.05% of the total reaction components.
The isocyanate prepolymer can be synthesized without adding a diluent, and a proper diluent can be added to adjust the viscosity. Suitable diluents include, but are not limited to, toluene, xylene, tetrahydrofuran, butyl acetate, and the like. The addition amount is 5-20%, preferably 10% or no addition of the total reaction components.
The synthesis of the isocyanate prepolymer can be carried out according to a synthesis method commonly used in the technical field of the existing polyurethane, for example, after the components of isocyanate and polymeric dihydric alcohol are mixed in proportion, the reaction is carried out for 4 to 6 hours at the temperature of 60 to 70 ℃ until the NCO percent content reaches the theoretical design value, and the modified curing agent is obtained.
The component B of the interpenetrating polymer network IPN-based double-component asparaguses polyurea coating is formed by compounding isocyanate prepolymer and IPDI monomer, and the weight compounding ratio of the isocyanate prepolymer and the IPDI monomer can be 8:2, preferably 9:1.
The preparation method of the component B of the double-component aspen polyurea coating based on the interpenetrating polymer network IPN can be carried out according to the following sequence:
1 mixing the isocyanate prepolymer and the IPDI uniformly in proportion.
2 adding proper diluent (the addition amount is 0-5% of the total amount of the component B) according to the requirement to adjust the viscosity, and stirring uniformly to obtain the component B.
The invention also relates to a preparation method of the double-component asparaguse coating based on the IPN, wherein the weight mixing ratio of A, B components is 1:0.5-0.4, the actual proportion is determined according to the amino and NCO content in the specific A, B component formula, and [ NCO ]/[ N ] = 1.15.
The invention further relates to a use method of the two-component asparaguses polyurea coating based on the interpenetrating polymer network IPN on the base surface of the low-surface-energy synthetic material.
The low surface energy synthetic materials include, but are not limited to, polypropylene Plastic (PP), polyethylene plastic (EP), ethylene Propylene Diene Monomer (EPDM), etc., and EPDM rubber is used as the low surface energy substrate in one example of the present invention.
Application of a two-component asparaurea coating based on an Interpenetrating Polymer Network (IPN) as a low-surface-energy substrate coating.
According to the invention, the double-component aspen polyurea coating based on the IPN can be directly coated on low-surface-energy base materials such as EPDM, PP and the like, and the base surface of the base material only needs simple polishing and cleaning, and does not need PP water priming paint or other base surface treatment technology. The concrete construction process is as follows:
1 the surface of the low surface energy substrate is uniformly polished by sand paper with the size of more than 800 meshes and cleaned.
2 the A, B components of the double-component asparagus polyurea coating based on the IPN provided by the invention are mixed in proportion and fully and uniformly stirred. Then adding a proper amount of diluent according to the requirement, and adjusting the spraying viscosity to be in the range of 18-25 seconds of coating-4 cups.
And 3, filling the mixed paint liquid with the adjusted viscosity into an air spray gun material tank for spraying, wherein the air pressure and the caliber size of a spray gun are adjusted according to common experience and habit in the technical field of coating.
4, the wet film after spraying can be solidified into a film after 12-24 hours at normal temperature, or is baked for 30 minutes at 80 ℃ to be solidified into a film.
Advantageous effects
1. So-called low surface energy materials, which are hydrophobic and oleophobic, have very low surface energy, such as polytetrafluoroethylene PTFE, and the adhesive is not easily wetted and is difficult to adhere to the surface of the polytetrafluoroethylene, so that the polytetrafluoroethylene is also called a non-stick coating. Common metals, concrete, etc. are high surface energy, so that general paints are easy to apply. However, for low surface energy materials, the coating needs to have lower surface tension than the low surface energy materials to be coated, so that the conventional coating has poor adhesion performance for low surface energy synthetic materials such as EPDM and PP, and therefore, in the conventional coating process, a water primer with high adhesion (PP water) needs to be coated first to increase the adhesion.
In the related art for solving the problem of the adhesion of the asparate polyurea coating, besides the traditional base surface treatment technologies such as base coating, surface polishing, sand blasting and the like, patent reports on modification of polyaspartate resin to improve the adhesion are also available. Such as: CN106854428 reports that the hydrogenated epoxy resin is used for modifying polyaspartic acid resin to prepare heavy anti-corrosion coating with good flexibility and strong adhesion with metal substrate. CN116836028 reports the synthesis of a novel polyaspartic ester resin from (dialkyl acyl) maleic acid monoester, which is said to significantly improve adhesion to metal substrates. CN20201057243.5 reports a polyaspartate resin doubly modified with silicone and epoxy groups, thereby improving the low temperature flexibility and bond strength of flexible anticorrosive coatings to concrete, metals, and composites. The above patent documents are all methods for improving the adhesion of the coating by introducing foreign groups into the polyaspartic ester resin structure, but the substrate is mostly metal or concrete material, which are all high surface energy materials, but low surface energy synthetic materials such as EPDM and PP are not mentioned. Indeed, to date, there have been few published reports of improving the adhesion of asparaguse coatings to low surface energy synthetic materials. Besides high adhesive force, the adhesive has high-temperature adhesion resistance, low-temperature elasticity, aging resistance, damp heat resistance, salt fog resistance and the like, so that the product quality requirement can be met; in practice, however, the modified polyaspartate resins may suffer from a decrease in other properties even if high adhesion is met.
Therefore, the synthesis of the paint with high adhesive force and high temperature adhesion resistance, low temperature elasticity, aging resistance, wet heat resistance and salt spray resistance on the low surface energy synthetic material is a technical problem which is difficult to solve in the technical field.
The polyurea modified polyaspartic ester resin provided by the invention improves the flexibility and the reactivity of the traditional alicyclic polyaspartic ester resin, so that the polyurea modified polyaspartic ester resin can provide better flexibility and adhesion when being used as a surface coating of a low-surface-energy synthetic material. Meanwhile, the polyoxypropylene ether segment in the polyurea structure can generate good compatibility with acrylate hydroxyalkyl ester, so that the compatibility between a first polymer phase (aliphatic polyurea phase) and a second polymer phase (acrylic copolymer phase) in the interpenetrating polymer network is increased. Thereby, the excellent aging resistance, impact resistance and low temperature flexibility of the polyurea polymer and the excellent adhesive property of the polyacrylate copolymer are exerted to the maximum extent.
The key points of the invention are as follows: and (3) a component A: a first polymeric aliphatic polyurea cross-link and a second polymeric polyacrylate copolymer, component B: the modified curing agent (such as B1) is not necessary.
Wherein the aliphatic polyurea crosslinks of the first polymer are synthesized from a polyurea modified polyaspartate, a polyaspartate, and an isocyanate curing agent, wherein the polyurea modified polyaspartate has a specific structure. The second polymeric polyacrylate copolymer is copolymerized from diacetone acrylamide, hydroxy alkyl acrylate, alkyl acrylate and organoboron amine complex initiator. The modified curing agent (B1) is synthesized by the components in a specific proportion.
Further:
the second polymer polyacrylate copolymer is prepared by using DAAM as a core monomer, and carrying out copolymerization reaction on hydroxyl alkyl acrylate, alkyl acrylate and an organoboron amine complex initiator to form the acrylate copolymer with strong adhesive force. Wherein: diacetone acrylamide (DAAM) is an N-substituted acrylamide derivative, and the molecule contains three functional groups of amido, carbonyl and double bond. The amide groups and carbonyl groups impart excellent cohesive properties to the polymer, while the double bonds may be copolymerized with other unsaturated monomers. The organoboron amine complex as an initiator for acrylate copolymers has three advantages: firstly, the polymerization initiated by organoborane is free radical polymerization initiated at the interface, and the surface of the low surface energy material can be oxidized to form active groups during the polymerization. This ensures that the polymer adheres well to low surface energy substrates. Secondly, the organoboron amine complex can be stably compatible and stored with other components in the component A related to the patent of the invention, so that the organoboron amine complex can be used as a latent initiator to realize the packaging of the two-component coating. Thirdly, the organoborane complex initiator has the advantage of low-temperature rapid initiation, and can meet the requirements of actual construction and coating of the coating.
2. The invention combines the IPDI curing agent monomer and the modified curing agent in the component B related to the invention, and utilizes the relatively high reactivity of the IPDI to enable the IPDI to rapidly react with primary amine components in the organoborane amine complex to form polyurea, thereby improving the decomplexing efficiency of the organoborane amine complex and further improving the initiation efficiency of the organoborane on the copolymerization of the acrylic ester monomer.
Drawings
FIG. 1 is an infrared spectrum of a polyurea prepolymer;
FIG. 2 type 104 polyurea modified polyaspartate (PUR-104) IR spectrum;
FIG. 3 IR spectrum of type 105 polyurea modified polyaspartate (PUR-105).
Detailed Description
The information of each main raw material used in the following examples is shown in table 1.
Table 1 examples are made with various major raw material specifications and manufacturers
Example 1 preparation of type 104 ureido modified polyaspartic acid ester (PUR-104)
First step polyurea prepolymer preparation
To a 2000ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a reflux tube and a constant pressure dropping funnel was charged 222.3 g (1 mol) of IPDI, and the air in the flask was replaced with nitrogen gas by vacuum and kept purged with nitrogen gas. A mixture of 287 g (0.5 mol) of AP-230S and 50 g of butyl acetate was slowly added dropwise via a constant pressure funnel while stirring, and the temperature of the reaction mass in the flask was controlled in the range of 30-40℃with a cold water bath for about 20-30 minutes. After the dripping is finished, the reaction is carried out for 1 hour at 40 ℃, then the temperature is raised to 60 ℃ for reaction for about 2 hours until the NCO percent content reaches 8.3 percent. Cooling to 40deg.C to obtain polyurea prepolymer (infrared spectrum shown in figure 1).
Second step preparation of PUR-104
The reaction of the first step described above was continued. 558 g (1 mol) of AP-104 resin and 50 g of butyl acetate are added into the reaction flask, after being stirred uniformly, 0.5 g of stannous octoate is added, nitrogen is introduced, the temperature is increased to 60 ℃ for constant temperature reaction for about 10 hours until NCO characteristic peaks (2270) -1 Nearby) disappears. The cooled PUR-104 (see FIG. 2 for an IR spectrum) with a solids content of 91% has an average amino equivalent of 1167.
Example 2 preparation of ureido modified polyaspartic acid ester of type 105 (PUR-105)
First step the first step of example 1
Preparation of second PUR-105
The reaction of the first step described above was continued. 580 g (1 mol) of AP-105 resin and 50 g of butyl acetate are added into the reaction flask, after being stirred uniformly, 0.5 g of stannous octoate is added, nitrogen is introduced, the temperature is increased to 60 ℃ for constant temperature reaction for about 10 hours until NCO characteristic peaks (2270) -1 Nearby) disappears. Cooled byPUR-105 having a solids content of 91%
(see FIG. 3 for an infrared spectrum) with an average amino equivalent of 1189.
Example 3 preparation of curative component B1
(1) Preparation of modified curing agent
200 g (0.32 mol) of HT-00, 108.49 g (0.65 mol) of HDI and 26,32 g (0.12 mol) of IPDI are added into a 1000ml four-neck flask with a stirring device, a thermometer, a nitrogen guide pipe and a reflux pipe, after stirring and mixing uniformly, 565.19 g (0.28 mol) of N220 and 4.5 g of stannous octoate are added, then air in the flask is replaced by nitrogen by vacuum, the nitrogen is kept to be introduced, and the temperature is raised to 60 ℃ for constant temperature reaction for 4-6 hours until NCO% reaches 9.2%.
And cooling to obtain the modified curing agent.
(2) Preparation of curing agent component B1
The modified curing agent prepared in the embodiment (1) and the IPDI monomer are uniformly mixed according to the weight ratio of 9:1, so as to obtain a curing agent component B1, wherein the average NCO% content is 12%.
Comparative example 1 preparation of curative component B2
(1) Preparation of modified curing agent
83.12 g (0.13 mol) of HT-00, 152.38 g (0.91 mol) of HDI and 41.56 g (0.19 mol) of IPDI are added into a 1000ml four-neck flask with a stirring device, a thermometer, a nitrogen guide pipe and a reflux pipe, after stirring and mixing uniformly, 622.95 g (0.31 mol) of N220 and 4.5 g of stannous octoate are added, then air in the flask is replaced by nitrogen by vacuum, the nitrogen is kept to be introduced, and the temperature is raised to 60 ℃ for constant temperature reaction for 4-6 hours until NCO% reaches 9.2%. And cooling to obtain the modified curing agent.
(2) Preparation of curing agent component B2
The modified curing agent prepared in the embodiment (1) and the IPDI monomer are uniformly mixed according to the weight ratio of 9:1, so as to obtain a curing agent component B2, wherein the average NCO% content is 12%.
Comparative example 2 preparation of curative component B3
200 g (0.32 mol) of HT-00, 108.49 g (0.65 mol) of HDI and 126,32 g (0.57 mol) of IPDI are added into a 1000ml four-neck flask with a stirring device, a thermometer, a nitrogen guide pipe and a reflux pipe, after stirring and mixing uniformly, 565.19 g (0.28 mol) of N220 and 5 g of stannous octoate are added, air in the flask is replaced by nitrogen by vacuum, the nitrogen is kept to be introduced, and the temperature is raised to 60 ℃ for constant temperature reaction for 4-6 hours until NCO% reaches 12%.
And cooling to obtain the modified curing agent B3.
Examples 4 to 7 and comparative examples 3 to 6 below are examples of the formulation of the component A (resin component) having different formulation compositions, the formulation composition information is shown in Table 2, and the raw material compositions are in parts by weight.
TABLE 2A component formulation list of different formulation compositions
Example 4 resin component formulation of A1 formulation
1 the raw material components with the formula numbers of 1-5 in the A1 in the table 2 are firstly mixed uniformly.
And 2, sequentially adding the raw material components with the serial numbers of 6-9 into the mixed solution, fully and uniformly stirring, and grinding the mixture to the fineness of less than or equal to 25 mu m by using a sand mill to prepare the gray color paste containing the resin component.
And 3, sequentially adding the raw material components with the serial numbers of 10-18 into the gray color paste, and stirring and dispersing for 30 minutes at a high speed (2000 rpm) to obtain the resin component of the A1 formula.
Example 5 resin component formulation of A2
According to the formulation of A2 in Table 2, the resin component of the A2 formulation was obtained by following the complete procedure of example 4.
Example 6 resin component formulation of A3
According to the formulation of A3 in Table 2, the resin component of the A3 formulation was obtained by following the complete procedure of example 4.
Example 7 resin component formulation of A4
According to the formulation of A4 in Table 2, the resin component of the A4 formulation was obtained by following the complete procedure of example 4.
Resin component formulation of comparative example 3A5
According to the formulation of A5 in Table 2, the resin component of the A5 formulation was obtained by following the complete procedure of example 4.
Resin component formulation of comparative example 4A6 formulation
According to the formulation of A6 in Table 2, the resin component of the A6 formulation was obtained by following the complete procedure of example 4.
Comparative example 5 resin component formulation of A7 the resin component of A7 formulation was prepared according to the formulation of A7 in table 2, and was prepared by following the complete procedure of example 4.
The following examples demonstrate the application of interpenetrating polymer network based two-component polyaspartic polyurea coatings provided by the present invention to Ethylene Propylene Diene Monomer (EPDM) base surfaces, wherein the surface of each 4A sized EPDM coupon was lightly sanded and cleaned with 800 grit sandpaper, and not PP water primer
Table 3 shows the proportions of the respective coating films composed of the A1-A7 resin components and the B1-B3 curing agent components and the results of their main property tests, each of the corresponding coating films being represented by F1-F11, respectively. The components are all calculated by weight.
Example 8
1 the components A1 and B1 are weighed according to the formula proportion of F1 in the table 3, and are fully stirred and uniformly mixed. Then adding proper amount of diluent according to the requirement, and adjusting the viscosity to be in the range of 18-25 seconds of coating-4 cups.
2, filling the mixed paint liquid with the adjusted viscosity into a SATA air spray gun, wherein the caliber of a nozzle is 2.0mm, and the air pressure is 3 kg/cm 2, 。
3 one spray coating to a wet film thickness of 85-90 μm on EPDM test strips.
And 4, standing the sprayed wet film test piece at room temperature for 25-20 minutes, and then placing the wet film test piece into an oven at 80 ℃ to bake for 30 minutes for curing and film forming to obtain a test piece F1. Performance was tested after 7 days of standing.
Examples 9 to 18
The corresponding A, B components were weighed according to the formulation proportions of F2-F11 in Table 3, and then the procedure of example 8 was followed to obtain test pieces F2-F11.
Table 3 Table A list of principal properties and compositions of the coating films in examples 9 to 18
Note that: OK indicates pass; NG indicates NO GOOD, i.e. does not pass.
As can be seen from Table 3, the coatings formed by mixing A1-A4 in F1-F4 with B1 and other materials respectively, wherein the polyurea modified polyaspartic ester resin PUR-104 or PUR-105 in A1-A4 has the same effect as the polyurea modified polyaspartic ester resin PUR-104 or PUR-105, and the polyurea modified polyaspartic ester resin PUR-104 or PUR-105 is mixed with AP-104 and DAAM according to the proportion shown in the table, and then B1 and other materials are added to synthesize the coating with good performance. It should be pointed out that the key point of the invention is that the paint formed by the mutual coordination of PUR-104 or PUR-105, AP-105 or AP-104, DAAM and B1 has the best adhesive force (grade 0) on the EPDM base material, and simultaneously, the paint has the advantages of high-temperature adhesion resistance, low-temperature elasticity, aging resistance, damp heat resistance and salt fog resistance, and meets the product quality requirement.
F5 A5 lacks DAAM, which breaks away from the EPDM substrate adhesion, failing.
In F6A 6 lacks polyurea modified polyaspartate resin PUR-104 or PUR-105, which is disqualified by detachment of adhesion to EPDM substrate.
In F7A 7 lacks AP-104 or AP-105, and its adhesion to EPDM substrate is released and failed.
F8 employs A1, but B2, rather than B1, has a class 1 adhesion to EPDM substrates that is lower than F1-F4.
F9 was A1, but B3 was used instead of B1, and the adhesive force on the EPDM substrate was released and failed.
F10 uses A2, but B2, rather than B1, has a class 1 adhesion to the EPDM substrate that is lower than F1-F4.
F11 was A2, but B3 was used instead of B1, and the adhesive force on the EPDM substrate was released, and failed.
The F7-F11 has disqualification in the aspects of high-temperature adhesion resistance, low-temperature elasticity, aging resistance, damp-heat resistance or salt fog resistance and the like.
Claims (10)
1. The double-component asparagus coating based on the IPN of the interpenetrating polymer network is characterized by comprising a component A and a component B;
the A component comprises an amino component of an aliphatic polyurea cross-linked polymer of a first polymer and a polyacrylate copolymer of a second polymer;
wherein the aliphatic polyurea cross-link of the first polymer is formed by cross-linking polyurea modified polyaspartate, polyaspartate and isocyanate curing agent; wherein the polyurea modified polyaspartate has a structural formula as shown in formula 1:
r in 1 1 A C1-C6 aliphatic chain alkylene, a cycloaliphatic alkylene, or a combination thereof; r is R 2 Alkylene groups, R, being isophorone diisocyanate, 6-methylene diisocyanate HDI or hydrogenated MDI 4 A linear alkylene group of 10 to 30 carbon atoms; r is R 3 、R 5 Hydrogen or a C1-C8 alkyl or ester group, respectively;
the polyacrylate copolymer of the second polymer is composed of: diacetone acrylamide, hydroxyl alkyl acrylate or alkyl acrylate, and organoboron amine complex;
the component B comprises: a combination of an isocyanate prepolymer and an isophorone diisocyanate monomer, which is the curative component of the aliphatic polyurea cross-link of the first polymer. Wherein the isocyanate prepolymer is formed by reacting compound isocyanate and polymeric dihydric alcohol, wherein the compound isocyanate comprises 55-65% by weight of 6-methylene diisocyanate trimer and 45-35% by weight of isophorone diisocyanate, 6-methylene diisocyanate or xylylene diisocyanate.
2. The two-component asparagus coating based on interpenetrating polymer network IPN according to claim 1,
the first polymer in the component A is polyurea modified polyaspartic ester in an aliphatic polyurea cross-linked polymer, and the polyaspartic ester is prepared by the following steps:
the first step is to condense difunctional amino compound and difunctional aliphatic isocyanate to obtain isocyanate-terminated polyurea prepolymer;
a second step of condensing the isocyanate-terminated polyurea prepolymer obtained in the first step with polyaspartic acid ester resin to obtain the polyurea modified polyaspartic acid ester;
in the first step, the difunctional amino compound is primary amino-terminated amine-terminated polyether and secondary amino-terminated amine-terminated polyether; the difunctional aliphatic isocyanate comprises isophorone diisocyanate, 6-methylene diisocyanate or xylylene diisocyanate; the equivalent ratio [ NCO ]/[ N ] of the synthesis of the aliphatic isocyanate and the difunctional amino compound is 2.05:1;
the polyaspartic acid ester resin in the second step comprises NH1420 and NH1520; the equivalent ratio [ NCO ]/[ N ] of the isocyanate-terminated polyurea prepolymer to the synthesis of the polyaspartic acid ester resin is 1:1.05.
3. The two-component asparagus coating based on interpenetrating polymer network IPN according to claim 1,
the hydroxy alkyl acrylate in the component A is hydroxy ethyl acrylate or hydroxy propyl acrylate;
the alkyl acrylate is methyl acrylate or ethyl acrylate;
the structural formula of the organoborane is shown as a formula 2,
wherein R is 1 、R 2 、R 3 Respectively isC1-C10 alkyl; am is a primary dibasic amine; v is 1-4:1.
4. The interpenetrating polymer network IPN-based two-component asparaurea coating according to claim 4, wherein said organoborane is triphenylborane, triethylborane, tri-n-propylborane, or tri-n-butylborane.
5. The interpenetrating polymer network IPN-based two-component asparate coating according to claim 1, wherein the polyurea modified polyaspartate is used in an amount of 20-40% by weight of the a component; the usage amount of the polyaspartic acid ester resin accounts for 20-40% of the component A; the use amount of diacetone acrylamide DAAM accounts for 15-35% of the component A, and the use amount of acrylic hydroxyalkyl accounts for 5-20% of the component A; the usage amount of the alkyl acrylate accounts for 0-10% of the component A; the boron content in the organoborane accounts for 0.05 to 0.8 percent of the component A.
6. The two-component asparagus coating based on interpenetrating polymer network IPN according to any one of claim 1 to 5,
the component A is prepared by the following steps: in terms of the weight percentage, the components are as follows,
(1) Firstly, uniformly stirring and mixing 20-30% of polyurea modified polyaspartic ester, 20-30% of polyaspartic ester resin, 5-10% of hydroxyl alkyl acrylate and 0-5% of alkyl acrylate;
(2) Adding diacetone acrylamide DAAM powder accounting for 15-20% of the total weight of the component A into the mixed solution, and fully stirring until the powder is completely dissolved;
(3) Weighing an organic boron amine complex, wherein the boron content A in the complex is 0.1-0.3% of the total weight of the component A, then adding the organic boron amine complex into the mixed solution, and uniformly stirring;
(4) Sequentially adding color paste, a leveling agent, a defoaming agent, a wetting agent, a dispersing agent, an antioxidant, an anti-aging agent, a filler and the like into the mixed solution according to the requirement of a paint formula, and stirring and dispersing for 30min at 2000 rpm; wherein the flatting agent, the antifoaming agent, the wetting agent, the dispersing agent, the antioxidant, the anti-aging agent and the like are used according to the recommended amounts of various suppliers, and the total amount of the components is not more than 3% of the total weight of the component A; the use amount of the color paste and the filler is 20-25% of the total weight of the component A;
(5) Adding 5-15% of solvent based on the total weight of the component A according to construction requirements, adjusting viscosity, and stirring uniformly to obtain the component A.
7. The interpenetrating polymer network IPN-based two-component aspen polyurea coating according to claim 1, wherein the isocyanate prepolymer in the B component is synthesized from a complex isocyanate and a polymeric diol in weight percent; wherein the composite isocyanate is formed by mixing 55-65% of HDI trimer and 35-45% of isophorone diisocyanate, 6-methylene diisocyanate or xylylene diisocyanate;
the equivalent ratio [ NCO ]/[ OH ] of the composite isocyanate to the polymeric dihydric alcohol is 3.0-6.0:1;
the polymeric glycol is polyether glycol or polyester glycol; the polyether glycol comprises polyoxypropylene glycol, ethylene oxide glycol and polytetrahydrofuran glycol which are used singly or after being mixed according to any proportion;
the polyester diol comprises polyadipate diol, polycaprolactone diol and polycarbonate diol which are used singly or after being mixed according to any proportion;
the weight compounding ratio of the isocyanate prepolymer to the isophorone diisocyanate monomer is 8:2.
8. The interpenetrating polymer network IPN-based two-component asparaurea coating according to claim 1, wherein the weight ratio of a to B components is 1:0.5-0.4.
9. The interpenetrating polymer network IPN-based two-component asparaurea coating according to claim 9, wherein the a and B components have [ NCO ]/[ N ] = 1.15 in terms of amino and NCO content.
10. Use of the two-component asparaguses coating based on interpenetrating polymer networks IPN according to claims 1-9 as a low surface energy substrate coating.
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| CN202311630277.8A CN117625022A (en) | 2023-12-01 | 2023-12-01 | Interpenetrating polymer network IPN-based two-component asparagus coating and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311630277.8A CN117625022A (en) | 2023-12-01 | 2023-12-01 | Interpenetrating polymer network IPN-based two-component asparagus coating and application thereof |
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