CN101368018A - Curing fluorine containing paint in normal temperature with quadric-polymerization - Google Patents

Curing fluorine containing paint in normal temperature with quadric-polymerization Download PDF

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Publication number
CN101368018A
CN101368018A CNA2007100726634A CN200710072663A CN101368018A CN 101368018 A CN101368018 A CN 101368018A CN A2007100726634 A CNA2007100726634 A CN A2007100726634A CN 200710072663 A CN200710072663 A CN 200710072663A CN 101368018 A CN101368018 A CN 101368018A
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acid
olefin
aliphatic
equal
containing coating
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CNA2007100726634A
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Chinese (zh)
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张振彬
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Abstract

The invention discloses normal temperature curing coating containing fluorine prepared through a quaternary-copolymerization method, and a preparation method thereof. The invention relates to a normal temperature curing coating containing fluorine prepared through a quaternary-copolymerization method, and a production method thereof. Currently, CTFE is commonly applied to prepare coatings, and the prepared products have poor stability and are easy to be crystallized. The components of the product comprise: TFE, fatty acid vinyl ester, aliphatic enol and aliphatic gadoleic acid, wherein, the solid accounts for 60 to 70 weight portions, the hydroxyl value is 40mgkoH/g to 75mgkoH/g, the acid value is 8mgkoH/g to 15mgkoH/g, after 4 is applied, the viscosity in a cup is 45s to 54s, and the proportion is 1.10 to 1.25; the ratio of the weight portions of the TFE, fatty acid vinyl ester, aliphatic enol and aliphatic gadoleic acid in the polymer is as follows: 35 to 45:25 to 40:12 to 18:2 to 3, and the chain-like structure is as follows: the normal alkyl of R1 equal to C1 to C3; R2 equal to (CH)n, n equal to 1 to 6; R3(CH2)n, n equal to 1 to 10. The invention is applied in indoor decoration and other fields.

Description

The ambient cure fluoro-containing coating and the making method of quarternary copolymerized method preparation
Technical field:
The present invention relates to ambient cure fluoro-containing coating of the quarternary copolymerized method preparation of a kind of usefulness and preparation method thereof.
Background technology:
Progress along with society, improving constantly of people's living standard, people also improve gradually to the requirement of domestic environment, use historical over and done with that lime whitewashes a wall in the past, coating is that everyone decorates the necessary a kind of material of family, but some shortcomings of modern coating have also exposed thereupon, and the widespread usage trifluorochloroethylene is made coating now, the product stability of using the manufacturing of this kind method is poor, easily crystallization.So eager needs can overcome the product birth of these shortcomings on the market.
Summary of the invention:
The present invention utilizes tetrafluoro vinylchlorid to replace trifluorochloroethylene, and the strong bond energy of tetrafluoro vinylchlorid CF is higher than the bond energy of trifluorochloroethylene C-Cl, makes the multipolymer Heat stability is good, and contamination resistance and unreactiveness are higher.
Above-mentioned purpose realizes by following technical scheme:
A kind of ambient cure fluoro-containing coating of quarternary copolymerized method preparation, its composition comprises: tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid, it is characterized in that: the shared parts by weight of solids content are 60~70, hydroxyl value is 40~75mgkoH/g, acid number is 8~15mgkoH/g, be coated with 4 one glasss of viscosity 45~54s, proportion is 1.10~1.25, described tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid at the shared ratio of weight and number of polymkeric substance are: 35~45:25~40:12~18:2~3, its chain schematic construction is: R 1=C 1~C 3Normal chain alkyl; R 2=(CH) n, n=1~6; R 3=(CH 2) n, n=1~10.
The making method of the ambient cure fluoro-containing coating of above-mentioned quarternary copolymerized method preparation, vinyl fatty ester, aliphatics enol, aliphatics olefin(e) acid and initiator are mixed, in the autoclave of-97kPa, vacuumize, vacuumize once more behind the inflated with nitrogen, suck tetrafluoro vinylchlorid and heat to 68~72 ℃, pressurization 500kPa~800kPa, it is 50% with solvent with the solids content dilution that reaction 20h forms multipolymer, be prepared into fluorine-containing paint vehicle, this material and pigment 3:1 mixed grinding fineness 25 μ m make finished product.
The making method of the ambient cure fluoro-containing coating of above-mentioned quarternary copolymerized method preparation, it is characterized in that: described initiator is a Diisopropyl azodicarboxylate, described solvent is dimethylbenzene, butylacetate or methyl iso-butyl ketone (MIBK).
This technical scheme has following beneficial effect
1. the present invention utilizes tetrafluoro vinylchlorid to replace trifluorochloroethylene, and the strong bond energy of tetrafluoro vinylchlorid CF is higher than the bond energy of trifluorochloroethylene C-Cl, makes the multipolymer Heat stability is good, and contamination resistance and unreactiveness are higher.The multi-component copolymer typing is quarternary copolymerized for this reason, is convenient to the parameter of multipolymer, and principal monomer and other monomeric ratio gap are dwindled, and can reduce the degree of crystallinity of multipolymer, improves the homogeneity of multipolymer in solvent.
The multipolymer high solids content be 60~70%, low viscosity (be coated with 4 one glasss of viscosity 45~54s), can be fine wetting, scattered with pigment, prevent that lacquer such as loose colour is sick, the paint film property that makes is superior.
3. the product hardness height that the present invention produced, softness, good luster and strong adhesion, anti-smog, chemicals-resistant, good weatherability.
4. this product is lacked at normal temperatures set time, reaches the maximum of paint standard, has remarkable resistant and self-cleaning property, can be made into the environment-friendly type marine antifouling coating, and the exterior coating, the aircraft anti-icing that also can be made into automobile case supercoat, self-cleaning are avenged coating etc.
5. because the atomic radius of fluoropolymer is little, polarizability is little, surface tension is little, so show resistance to bond, and fluoro-resin has less internal cohesive energy and low-friction coefficient, and the base-material as wear proof lubricating painting materials is equipped with lubricant, its wear-resisting lubricity is then more outstanding, so be widely used in industries such as mould, cooker, household electrical appliances, machinery equipment.Also can be used for outdoor long-acting, high-decoration protective cover.
6. fluoro-containing coating has good weathering resistance; good guarantor's light tint retention energy is difficult for efflorescence, good luster; fluorochemical urethane coating has good moisture-proof and ultraviolet-resistant performance, is widely used in the protection of aircraft skin, car paint, large storage tank surface and stone artifact.
The specific embodiment of the present invention:
Embodiment 1:
A kind of ambient cure fluoro-containing coating of quarternary copolymerized method preparation, its composition comprises: tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid, solids content is 70%, hydroxyl value is 75mgkoH/g, acid number is 15mgkoH/g, is coated with 4 one glasss of viscosity 54s, and proportion is 1.25, described tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid at the shared ratio of weight and number of polymkeric substance are: 45:40:18:3, its chain schematic construction is: R 1=C 1~C 3Normal chain alkyl; R 2=(CH) n, n=6; R 3=(CH 2) n, n=10.
Embodiment 2:
A kind of ambient cure fluoro-containing coating of quarternary copolymerized method preparation, its composition comprises: tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid, solids content is 65%, hydroxyl value is 65mgkoH/g, acid number is 10mgkoH/g, is coated with 4 one glasss of viscosity 50s, and proportion is 1.20, described tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid at the shared ratio of weight and number of polymkeric substance are: 40:30:14:3, its chain schematic construction is: R 1=C 1~C 3Normal chain alkyl; R 2=(CH) n, n=5; R 3=(CH 2) n, n=7.
Embodiment 3:
A kind of ambient cure fluoro-containing coating of quarternary copolymerized method preparation, its composition comprises: tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid, solids content is 60%, hydroxyl value is 40mgkoH/g, acid number is 8mgkoH/g, is coated with 4 one glasss of viscosity 45s, and proportion is 1.10, described tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid at the shared ratio of weight and number of polymkeric substance are: 35:25:12:2, its chain schematic construction is: R 1=C 1~C 3Normal chain alkyl; R 2=(CH) n, n=1; R 3=(CH 2) n, n=1.
Embodiment 4:
The making method of the ambient cure fluoro-containing coating of quarternary copolymerized method preparation: vinyl fatty ester, aliphatics enol, aliphatics olefin(e) acid and Diisopropyl azodicarboxylate are mixed, in the autoclave of-97kPa, vacuumize, vacuumize once more behind the inflated with nitrogen, sucking tetrafluoro vinylchlorid heats to 72 ℃, pressurization 800kPa, it is 50% with dimethylbenzene with the solids content dilution that reaction 20h forms multipolymer, is prepared into fluorine-containing paint vehicle, and this material and pigment 3:1 mixed grinding fineness 25 μ m make finished product.
Embodiment 5:
The making method of the ambient cure fluoro-containing coating of quarternary copolymerized method preparation: vinyl fatty ester, aliphatics enol, aliphatics olefin(e) acid and Diisopropyl azodicarboxylate are mixed, in the autoclave of-97kPa, vacuumize, vacuumize once more behind the inflated with nitrogen, sucking tetrafluoro vinylchlorid heats to 68, pressurization 500kPa, it is 50% with butylacetate with the solids content dilution that reaction 20h forms multipolymer, is prepared into fluorine-containing paint vehicle, and this material and pigment 3:1 mixed grinding fineness 25 μ m make finished product.
Embodiment 6:
The making method of the ambient cure fluoro-containing coating of quarternary copolymerized method preparation: vinyl fatty ester, aliphatics enol, aliphatics olefin(e) acid and Diisopropyl azodicarboxylate are mixed, in the autoclave of-97kPa, vacuumize, vacuumize once more behind the inflated with nitrogen, sucking tetrafluoro vinylchlorid heats to 70 ℃, pressurization 700kPa, it is 50% with methyl iso-butyl ketone (MIBK) with the solids content dilution that reaction 20h forms multipolymer, is prepared into fluorine-containing paint vehicle, and this material and pigment 3:1 mixed grinding fineness 25 μ m make finished product.
Embodiment 7:
The performance index of this product:
Viscosity 45~54s
Do not have in 4 weeks of alkali resistance (15%NaOH) and change
Shock-resistance 50/cm
1 grade of sticking power
Gloss (60 degree) 85
Hardness 0.8

Claims (3)

1. the ambient cure fluoro-containing coating of a quarternary copolymerized method preparation, its composition comprises: tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid, it is characterized in that: the shared parts by weight of solids content are 60~70, hydroxyl value is 40~75mgkoH/g, acid number is 8~15mgkoH/g, be coated with 4 one glasss of viscosity 45~54s, proportion is 1.10~1.25, described tetrafluoro vinylchlorid, vinyl fatty ester, aliphatic olefin alcohols and fatty olefin(e) acid at the shared ratio of weight and number of polymkeric substance is: 35~45:25~40:12~18:2~3, its chain schematic construction is: R 1=C 1~C 3Normal chain alkyl; R 2=(CH) n, n=1~6; R 3=(CH 2) n, n=1~10.
2. the making method of the ambient cure fluoro-containing coating of the described quarternary copolymerized method preparation of a claim 1, it is characterized in that: with vinyl fatty ester, the aliphatics enol, aliphatics olefin(e) acid and initiator are got material according to the above ratio, mix, in the autoclave of-97kPa, vacuumize, vacuumize once more behind the inflated with nitrogen, the tetrafluoro vinylchlorid that sucks respective amount is heated to 68~72 ℃, pressurization 500kPa~800kPa, it is 50% with solvent with the solids content dilution that reaction 20h forms multipolymer, be prepared into fluorine-containing paint vehicle, this material and pigment 3:1 mixed grinding fineness 25 μ m make finished product.
3. the making method of the ambient cure fluoro-containing coating of quarternary copolymerized method preparation according to claim 2, it is characterized in that: described initiator is a Diisopropyl azodicarboxylate, described solvent is dimethylbenzene, butylacetate or methyl iso-butyl ketone (MIBK).
CNA2007100726634A 2007-08-16 2007-08-16 Curing fluorine containing paint in normal temperature with quadric-polymerization Pending CN101368018A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140018492A1 (en) * 2011-03-31 2014-01-16 Daikin Industries, Ltd. Solvent-based paint composition and fluorine-containing copolymer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140018492A1 (en) * 2011-03-31 2014-01-16 Daikin Industries, Ltd. Solvent-based paint composition and fluorine-containing copolymer
US9920214B2 (en) * 2011-03-31 2018-03-20 Daikin Industries, Ltd. Solvent-based paint composition and fluorine-containing copolymer

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