阅读说明：本技术 一种全卤二烯烃改性聚合物防腐涂料 (Perhalodiolefine modified polymer anticorrosive paint ) 是由 钟震 张广达 蒋拥华 于 2020-12-31 设计创作，主要内容包括：本发明涉及涂料技术领域,具体涉及到一种全卤二烯烃改性聚合物防腐涂料。其制备原料,以重量份计,包括如下组分：卤化二烯烃改性聚合物10-30、丙烯酸树脂5-20、氯化石蜡3-10、填料10-20、分散剂0-1、防沉剂0-1、溶剂20-40。本发明中的全卤二烯烃改性聚合物防腐涂料中采用含有全氯代二烯烃接枝改性的二烯类橡胶作为成膜物,树脂本身较高的卤素含量,赋予了树脂优良的附着力、耐高温、耐腐蚀性能。(The invention relates to the technical field of coatings, in particular to a perhalo diene modified polymer anticorrosive coating. The preparation raw materials comprise the following components in parts by weight: 10-30 parts of halogenated diene modified polymer, 5-20 parts of acrylic resin, 3-10 parts of chlorinated paraffin, 10-20 parts of filler, 0-1 part of dispersant, 0-1 part of anti-settling agent and 20-40 parts of solvent. The perchlorodiene-containing graft-modified diene rubber is used as a film forming material in the perhalogenated diene modified polymer anticorrosive paint, and the resin has high halogen content, so that the resin has excellent adhesive force, high temperature resistance and corrosion resistance.)

1. The perhalogenated diene modified polymer anticorrosive paint is characterized by comprising the following components in parts by weight:

halogenated diene modified polymer 10-30

Acrylic resin 5-20

Chlorinated paraffin 3-10

10-20 parts of filler

0 to 1 part of dispersant

0-1 part of anti-settling agent

20-40 parts of solvent.

2. The perhalo diene modified polymer anticorrosive paint according to claim 1, wherein the halogenated diene used in the halogenated diene modified polymer is a halogenated conjugated diene.

3. The perhalo diene modified polymer anticorrosive paint according to claim 2, wherein the halogenated conjugated diene is a perhalogenated cyclic conjugated diene.

4. The perhalo diene modified polymer anticorrosive coating of claim 3, wherein the perhalocyclic conjugated diene is selected from one or more of hexafluorocyclopentadiene, hexabromocyclopentadiene, hexachlorocyclopentadiene.

5. The perhalo diene modified polymer anticorrosive paint according to claim 1, wherein the halogenated diene modified polymer is a halogenated conjugated diene grafted unsaturated polymer; the unsaturated polymer is selected from one or more of polyisoprene, butadiene homopolymer, butadiene-styrene copolymer and styrene-isoprene-butadiene copolymer.

6. The perhalo diene modified polymer anticorrosive paint according to claim 5, wherein the halogenated conjugated diene grafted unsaturated polymer has a halogenated conjugated diene grafting ratio of not less than 20%.

7. The perhalo diene modified polymer anticorrosive paint according to claim 6, wherein the halogenated conjugated diene grafted unsaturated polymer has a halogenated conjugated diene grafting ratio of not less than 40%.

8. The perhalo diene modified polymer anticorrosive paint according to any one of claims 1 to 7, wherein the solvent is xylene and aromatic solvent oil, and the weight ratio of the perhalo diene modified polymer anticorrosive paint is (2-3): 1.

9. the perhalo diene modified polymer anticorrosive paint according to claim 8, wherein the filler is talcum powder and precipitated barium sulfate, and the weight ratio of the filler is (1-3): 1.

10. the perhalo diene modified polymer anticorrosive paint according to any one of claims 1 to 7, wherein the anti-settling agent is modified organic bentonite.

Technical Field

The invention relates to the technical field of coatings, in particular to a perhalo diene modified polymer anticorrosive coating.

Background

Materials such as steel are widely used in industry and daily life, and cause more economic loss due to chemical corrosion, electrochemical corrosion and the like. By adopting a proper anticorrosion technology, the corrosion of metal is slowed down and controlled, thereby being beneficial to the sustainable utilization of resources and reducing loss.

The coating is an important material for corrosion prevention, can form a firmly attached interface on the surface of a substrate, enables the substrate not to be corroded by various corrosive media (such as water in the atmosphere and acid and alkali), and reduces mechanical damage on the surface of an object, thereby prolonging the service life. Halogen-containing polymers are widely used for their excellent corrosion resistance, such as chlorinated rubber and chloroprene rubber. However, the application range of the anticorrosive material in the prior art needs to be further expanded, and the adhesion performance, the corrosion resistance, the high temperature resistance and the like need to be further improved.

Disclosure of Invention

In order to solve the technical problems, the first aspect of the invention provides a perhalogenated diene modified polymer anticorrosive paint, which comprises the following raw materials in parts by weight:

as a preferred technical solution of the present invention, the halogenated diene used in the halogenated diene modified polymer is halogenated conjugated diene.

As a preferred technical scheme of the invention, the halogenated conjugated diene is perhalogenated cyclic conjugated diene.

As a preferable technical scheme of the invention, the perhalogenated cyclic conjugated diene is one or more selected from hexafluorocyclopentadiene, hexabromocyclopentadiene and hexachlorocyclopentadiene.

As a preferred technical scheme of the invention, the halogenated diene modified polymer is a halogenated conjugated diene grafted unsaturated polymer; the unsaturated polymer is selected from one or more of polyisoprene, butadiene homopolymer, butadiene-styrene copolymer and styrene-isoprene-butadiene copolymer.

As a preferred technical scheme of the invention, the halogenated conjugated diene grafting rate of the halogenated conjugated diene grafted unsaturated polymer is not less than 20%.

As a preferred technical scheme of the invention, the halogenated conjugated diene grafting rate of the halogenated conjugated diene grafted unsaturated polymer is not less than 40%.

As a preferable technical scheme of the invention, the solvent is xylene and aromatic solvent naphtha, and the weight ratio of the xylene and aromatic solvent naphtha is (2-3): 1.

as a preferable technical scheme of the invention, the filler is talcum powder and precipitated barium sulfate, and the weight ratio of the filler is (1-3): 1.

as a preferable technical scheme of the invention, the anti-settling agent is modified organic bentonite.

Has the advantages that: the perchlorodiene-containing graft-modified diene rubber is used as a film forming material in the perhalogenated diene modified polymer anticorrosive paint, and the resin has high halogen content, so that the resin has excellent adhesive force, high temperature resistance and corrosion resistance.

Detailed Description

The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

It should be understood that other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about".

The invention provides a perhalogenated diene modified polymer anticorrosive paint, which comprises the following components in parts by weight:

the perhalogenated diene modified polymer anticorrosive paint is prepared by mainly taking halogenated diene modified polymer as a film forming substance and combining the interaction among components such as acrylic resin, specific filler, solvent and the like, so that the anticorrosive paint with excellent comprehensive performance is prepared.

The halogenated diene modified polymer is obtained by reacting halogen-substituted diene with polymers containing unsaturated building in some structures. The modification method, preparation method and the like of the halogenated diene modified polymer in the invention are not particularly limited, and the halogenated diene modified polymer can be prepared by technical means well known to those skilled in the art, for example, an initiator can be added, and the halogenated diene modified polymer can be prepared by a mike addition reaction.

In some embodiments, the halogenated diene employed in the halogenated diene modified polymer is a halogenated conjugated diene. The halogenated conjugated diene in the invention is a diene obtained by substituting diene with a structure containing two carbon-carbon double bonds and two double bonds separated by a single bond by halogen atoms such as fluorine atom, chlorine atom, bromine atom and the like.

In some preferred embodiments, the halogenated conjugated diene is a perhalogenated cyclic conjugated diene.

Further preferably, the perhalogenated cyclic conjugated diene is one or more selected from hexafluorocyclopentadiene, hexabromocyclopentadiene and hexachlorocyclopentadiene. In addition, the perhalogenated cyclic conjugated diene of the present invention may be a derivative obtained by substituting a hydrogen atom in the cyclopentadiene structure with a combination of a fluorine atom, a chlorine atom and a bromine atom.

In some embodiments of the invention, the halogenated conjugated diene in the halogenated diene modified polymer grafts the unsaturated polymer. The specific kind of the unsaturated polymer in the present invention is not particularly limited, and various unsaturated polymers known to those skilled in the art can be selected.

In some preferred embodiments, the unsaturated polymer is selected from one or more of polyisoprene, butadiene homopolymer, butadiene-styrene copolymer, styrene-isoprene-butadiene copolymer. High cis polybutadiene is exemplified herein, wherein the cis structure is greater than 99%.

In some embodiments, the halogenated conjugated diene grafted unsaturated polymer has a halogenated conjugated diene grafting ratio of not less than 20%.

Further, the halogenated conjugated diene grafting ratio of the halogenated conjugated diene grafting unsaturated polymer is not less than 40%.

Further preferably, the halogenated conjugated diene graft ratio of the halogenated conjugated diene graft unsaturated polymer is not less than 50%.

The grafting rate of the halogenated conjugated diene in the invention refers to the molar content of the halogenated conjugated diene grafted on the unsaturated polymer through reaction, wherein the percentage refers to the molar percentage, and the grafting rate can be determined by testing the halogen content in the polymer in a nuclear magnetic and infrared lamp mode. The applicant has found that the use of halogenated diene modified polymers with higher grafting ratio can significantly improve the corrosion resistance of the coating, however, too high grafting ratio can cause significant reduction of adhesion to the surface of the substrate.

In some embodiments, the solvent is xylene and aromatic solvent oil, and the weight ratio of the xylene to the aromatic solvent oil is (2-3): 1. further preferably, the solvent is xylene and aromatic solvent oil, and the weight ratio of the xylene to the aromatic solvent oil is 2.5: 1.

the aromatic hydrocarbon solvent oil with high boiling point has the characteristics of proper distillation range and volatility, strong dissolving power, low smell and the like. High boiling aromatic solvent oils well known to those skilled in the art, such as S-800, and the like, may be selected for use in the present invention.

The filler in the invention refers to a material filled in other objects. In chemical products, the filler is also called filler, which is a solid material for improving processability and mechanical properties of products and/or reducing cost.

In some embodiments, the filler is talc powder and precipitated barium sulfate, and the weight ratio of the talc powder to the precipitated barium sulfate is (1-3): 1.

barium sulfate has the advantages of strong chemical inertness, good stability, acid and alkali resistance, moderate hardness, high specific gravity, high whiteness, capability of absorbing harmful rays and the like, is a material with an environment-friendly function, and is widely applied to the fields of various coatings, medium and high grade printing ink, pharmaceutical synthesis chemical industry, rubber, papermaking, ceramics, cosmetics and the like. When the product is used for rubber and plastic products, the properties of hardness, strength, rigidity, wear resistance, high temperature resistance, acid and alkali resistance, ultraviolet resistance, water resistance and the like of the products are improved, the surface aging is prevented, and the cost of the products is reduced.

Preferably, the particle size of the precipitated barium sulfate is 0.1-0.3 μm.

More preferably, the barium sulfate is purchased from Jiaxin chemical industry and has a particle size of 0.1 μm.

The main component of the talcum powder is hydrous magnesium silicate, and the talcum powder is prepared by crushing, then treating with hydrochloric acid, washing with water and drying.

Further preferably, the filler is talcum powder and precipitated barium sulfate, and the weight ratio of the filler is 2: 1. the applicant finds that by adopting the talcum powder and the precipitated barium sulfate in the proportion, the high-temperature resistance of the coating can be remarkably improved, so that the coating can bear longer time in an environment of 130 ℃.

In some embodiments, the anti-settling agent is a modified organobentonite. The modified organic bentonite is water-based rheology modified organic bentonite, and has the advantages of electrolyte stability, emulsion stability, stability in electrophoretic coating application, prevention of hard precipitation of pigments or fillers, reduction of water shrinkage, and reduction of color separation and blooming phenomena. Various modified organobentonites known to those skilled in the art can be used, for example Bentoni EW from Kehn chemical.

The chlorinated paraffin in the invention is an organic substance derived from chlorination of paraffin hydrocarbon. Is a mixture of chlorinated derivatives obtained by free radical reaction of straight chain alkane with different carbon numbers of C10-C30 through chlorine, the chlorine content of general products is 40-70 percent of chemical book, and the products with the chlorine content of 40-52 percent at normal temperature are light yellow viscous liquid; 54-60% of the mixture is viscous yellow semisolid matter; 70% of the resin is brittle resin-like solid. The chlorinated paraffin is odorless, nontoxic, flame-retardant and low-volatility viscous liquid, has low volatility and good electrical insulation property, is insoluble in water, ethanol, glycol and glycerol, and is soluble in aliphatic hydrocarbon, aromatic hydrocarbon, chlorides thereof and the like.

In some embodiments, the chlorinated paraffin is a mixture of chlorinated paraffin 52 and chlorinated paraffin 70 in a 1:1 weight ratio. The applicant finds that the chlorinated paraffin with the proportion is beneficial to obviously improving the leveling property of the coating, so that the chlorinated paraffin can be well spread and wetted on the surface of a base material, and the adhesion of the coating to the surface of the base material is obviously improved.

The dispersing agent is a high molecular compound component containing hydrophobic groups and hydrophilic groups in a molecular structure, and can fully disperse components such as fillers, acrylic resin, halogenated diene modified polymers and the like in a coating system, so that the problems of agglomeration of the components and the like are avoided. The specific components and sources of the dispersant in the present invention are not particularly limited, and various dispersant components known to those skilled in the art may be selected and commercially available. The dispersant BYK-P104S is a preferable technical scheme.

The acrylic resin in the present invention is a generic term for polymers of acrylic acid, methacrylic acid and derivatives thereof. The invention selects thermoplastic acrylic resin, which is a kind of thermoplastic resin prepared by polymerizing acrylic acid, methacrylic acid and derivatives (such as esters, nitriles and amides) thereof. The softening by heating and the solidification by cooling can be repeated. The general linear high molecular compound can be a homopolymer or a copolymer, and has good physical and mechanical properties, excellent weather resistance, chemical resistance and water resistance, and high light and color retention. Various acrylic resins known to those skilled in the art may be selected and commercially available, such as L7250 for top size paints.

Under the premise of not influencing the comprehensive performance of the anticorrosive paint, other auxiliary agents such as an antioxidant, a pigment and the like can be added. In some preferred embodiments, the pigment is titanium dioxide; further preferably, the titanium dioxide is diamond titanium dioxide.

The method for preparing the anticorrosive paint in the present invention is particularly limited, and the anticorrosive paint may be prepared and used in a manner known to those skilled in the art, and for example, the anticorrosive paint may be prepared by mixing and defoaming the raw materials for preparing the paint in a conventional manner.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

Examples

Example 1: the embodiment discloses a perhalo diene modified polymer anticorrosive paint which comprises the following raw materials in parts by weight:

halogenated diene modified Polymer 28

Acrylic resin 13

Chlorinated paraffin 6

Talc powder 12

Barium sulfate 6

Diamond type titanium dioxide 13

Dispersant 0.5

Anti-settling agent 0.6

And (4) a solvent 25.

The halogenated diene modified polymer is hexachlorocyclopentadiene grafted cis-1, 4-polybutadiene rubber, and the grafting rate is 50%; the acrylic resin is thermoplastic acrylic resin L7250; the chlorinated paraffin is a mixture of chlorinated paraffin 52 and chlorinated paraffin 70, and the weight ratio of the chlorinated paraffin is 1: 1; the barium sulfate is purchased from Jiaxin chemical industry, and the particle size is 0.1 mu m; the dispersant is BYK-P104S; the modified organic bentonite Bentonie EW is prepared by the following steps of (1) preparing modified organic bentonite Bentonie EW; the solvent is xylene and aromatic solvent oil (S-800), and the weight ratio of the xylene and aromatic solvent oil is 2.5: 1.

example 2: the embodiment discloses a perhalo diene modified polymer anticorrosive paint which comprises the following components in parts by weight：

Halogenated diene modified Polymer 21

Acrylic resin 13

Chlorinated paraffin 6

Talc powder 12

Barium sulfate 6

Diamond type titanium dioxide 13

Dispersant 0.5

Anti-settling agent 0.6

And (4) a solvent 25.

The halogenated diene modified polymer is hexachlorocyclopentadiene grafted cis-1, 4-polybutadiene rubber, and the grafting rate is 20%; the acrylic resin is thermoplastic acrylic resin L7250; the chlorinated paraffin is a mixture of chlorinated paraffin 52 and chlorinated paraffin 70, and the weight ratio of the chlorinated paraffin is 1: 1; the barium sulfate is purchased from Jiaxin chemical industry, and the particle size is 0.1 mu m; the dispersant is BYK-P104S; the modified organic bentonite Bentonie EW is prepared by the following steps of (1) preparing modified organic bentonite Bentonie EW; the solvent is xylene and aromatic solvent oil (S-800), and the weight ratio of the xylene and aromatic solvent oil is 2.5: 1.

example 3: the embodiment discloses a perhalo diene modified polymer anticorrosive paint which comprises the following raw materials in parts by weight:

halogenated diene modified Polymer 21

Acrylic resin 13

Chlorinated paraffin 6

Talc powder 12

Barium sulfate 6

Diamond type titanium dioxide 13

Dispersant 0.5

Anti-settling agent 0.6

And (4) a solvent 25.

The halogenated diene modified polymer is hexachlorocyclopentadiene grafted cis-1, 4-polybutadiene rubber, and the grafting rate is 50%; the acrylic resin is thermoplastic acrylic resin L7250; the chlorinated paraffin is a mixture of chlorinated paraffin 52 and chlorinated paraffin 70, and the weight ratio of the chlorinated paraffin is 1: 1; the barium sulfate is purchased from Jiaxin chemical industry, and the particle size is 0.1 mu m; the dispersant is BYK-P104S; the modified organic bentonite Bentonie EW is prepared by the following steps of (1) preparing modified organic bentonite Bentonie EW; the solvent is xylene and aromatic solvent oil (S-800), and the weight ratio of the xylene and aromatic solvent oil is 2.5: 1.

example 4: the embodiment discloses a perhalo diene modified polymer anticorrosive paint which comprises the following raw materials in parts by weight:

halogenated diene modified Polymer 28

Acrylic resin 13

Chlorinated paraffin 6

Barium sulfate 18

Diamond type titanium dioxide 13

Dispersant 0.5

Anti-settling agent 0.6

And (4) a solvent 25.

The halogenated diene modified polymer is hexachlorocyclopentadiene grafted cis-1, 4-polybutadiene rubber, and the grafting rate is 50%; the acrylic resin is thermoplastic acrylic resin L7250; the chlorinated paraffin is a mixture of chlorinated paraffin 52 and chlorinated paraffin 70, and the weight ratio of the chlorinated paraffin is 1: 1; the barium sulfate is purchased from Jiaxin chemical industry, and the particle size is 0.1 mu m; the dispersant is BYK-P104S; the modified organic bentonite Bentonie EW is prepared by the following steps of (1) preparing modified organic bentonite Bentonie EW; the solvent is xylene and aromatic solvent oil (S-800), and the weight ratio of the xylene and aromatic solvent oil is 2.5: 1.

example 5: the embodiment discloses a perhalo diene modified polymer anticorrosive paint which comprises the following raw materials in parts by weight:

halogenated diene modified Polymer 28

Acrylic resin 13

Chlorinated paraffin 6

Talc powder 12

Barium sulfate 6

Diamond type titanium dioxide 13

Dispersant 0.5

Anti-settling agent 0.6

And (4) a solvent 25.

The halogenated diene modified polymer is hexachlorocyclopentadiene grafted cis-1, 4-polybutadiene rubber, and the grafting rate is 50%; the acrylic resin is thermoplastic acrylic resin L7250; the chlorinated paraffin is chlorinated paraffin 52; the barium sulfate is purchased from Jiaxin chemical industry, and the particle size is 0.1 mu m; the dispersant is BYK-P104S; the modified organic bentonite Bentonie EW is prepared by the following steps of (1) preparing modified organic bentonite Bentonie EW; the solvent is xylene and aromatic solvent oil (S-800), and the weight ratio of the xylene and aromatic solvent oil is 2.5: 1.

example 6: the embodiment discloses a perhalo diene modified polymer anticorrosive paint which comprises the following raw materials in parts by weight:

halogenated diene modified Polymer 28

Acrylic resin 13

Chlorinated paraffin 6

Talc powder 12

Barium sulfate 6

Diamond type titanium dioxide 13

Dispersant 0.5

Anti-settling agent 0.6

And (4) a solvent 25.

The halogenated diene modified polymer is hexachlorocyclopentadiene grafted cis-1, 4-polybutadiene rubber, and the grafting rate is 50%; the acrylic resin is thermoplastic acrylic resin L7250; the chlorinated paraffin is a mixture of chlorinated paraffin 52 and chlorinated paraffin 70, and the weight ratio of the chlorinated paraffin is 1: 1; the barium sulfate is purchased from Jiaxin chemical industry, and the particle size is 0.1 mu m; the dispersant is BYK-P104S; the modified organic bentonite Bentonie EW is prepared by the following steps of (1) preparing modified organic bentonite Bentonie EW; the solvent is xylene.

Example 7: the embodiment discloses a perhalo diene modified polymer anticorrosive paint which comprises the following raw materials in parts by weight:

halogenated diene modified Polymer 28

Acrylic resin 13

Chlorinated paraffin 6

Talc powder 18

Diamond type titanium dioxide 13

Dispersant 0.5

Anti-settling agent 0.6

And (4) a solvent 25.

The halogenated diene modified polymer is hexachlorocyclopentadiene grafted cis-1, 4-polybutadiene rubber, and the grafting rate is 50%; the acrylic resin is thermoplastic acrylic resin L7250; the chlorinated paraffin is a mixture of chlorinated paraffin 52 and chlorinated paraffin 70, and the weight ratio of the chlorinated paraffin is 1: 1; the dispersant is BYK-P104S; the modified organic bentonite Bentonie EW is prepared by the following steps of (1) preparing modified organic bentonite Bentonie EW; the solvent is xylene and aromatic solvent oil (S-800), and the weight ratio of the xylene and aromatic solvent oil is 2.5: 1.

performance testing

The applicant carries out relevant performance tests on the anticorrosive paint in the embodiment, and carries out adhesion tests, salt spray resistance and high temperature resistance (130 ℃) tests mainly according to the following national standards GB/T5210 and GB/T1771, and the test results are shown in the following table 1.

TABLE 1

	Adhesion force	Salt spray resistance/h	High temperature resistance/h
				Example 1	Level 0	1560	160
Example 2	Grade 3	900	80
				Example 3	Level 1	1340	136
Example 4	Level 1	1375	94
				Example 5	Stage 2	1480	103
Example 6	Stage 2	1060	74
				Example 7	Level 0	1350	91

The experimental results show that the anticorrosive coating disclosed by the invention has excellent adhesive force to a metal base material, can resist high temperature for a longer time, and has excellent salt spray resistance.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.