CN86106365A - The preparation method of polyolefine chloride coatings - Google Patents
The preparation method of polyolefine chloride coatings Download PDFInfo
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- CN86106365A CN86106365A CN 86106365 CN86106365A CN86106365A CN 86106365 A CN86106365 A CN 86106365A CN 86106365 CN86106365 CN 86106365 CN 86106365 A CN86106365 A CN 86106365A CN 86106365 A CN86106365 A CN 86106365A
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Abstract
With the pretreated high-density polyethylene powder body of degrading, in the presence of separant, under near the temperature the poly fusing point, carry out gas-solid phase chlorination reaction, make cl content and be 45-70% chlorinatedpolyethylene, dissolve in toluene-acetone-n-butyl acetate mixed solvent, solid content is that the viscosity of 20% solution is about 30 seconds (being coated with-4 glasss), hardness of film is 0.58 (t/to), snappiness is passed through for diameter of axle 2mm, shock strength 50kgcm, sticking power one-level (drawing the circle method).
Description
The present invention proposes a kind of method for preparing polyolefine chloride coatings, it belongs to macromolecule modified field.
Chlorinated polymer has good performances such as weather-proof, anti-combustion, oil resistant and chemical-resistant resistance.The coating made from it has purposes widely in machinery, chemical industry, car and boat manufacturing and building industry.
Adopting chlorinatedpolyolefins is highly significant as the raw material of preparation coating to the development of coatings industry.Because polyolefine is the Industrial products of scale operation, China can produce 1,000,000 tons polyethylene and multipolymer thereof during seven, five.With they raw materials, can open up the new Application Areas of polyethylene as chlorization product.But will prepare on the chlorinatedpolyolefins that is suitable on the coating is being produced still has a lot of problems to await solving.The chlorinatedpolyethylene (Ger(east) 116 that solution method is produced, 242(1975)), its product performance can adapt to the requirement of coating, but this method will consume a large amount of organic solvents, thereby the production cost height, solvent all can work the mischief to human body and environment simultaneously.Recently, (day disclosure special permission 129 of the solubility chloride coatings polyethylene of Japan Showa Denko K. K exploitation, 004(1983)), it is produced with water phase suspension, though the quality of product still can adapt to the requirement of coating, but the chlorinity of product is lower, and range of application must be restricted.In addition, equipment corrosion and three deserted citys were more serious when the water method was produced, neither the ideal production method.Solid phase method production chlorinatedpolyolefins production cost is low, and the harm of the equipment corrosion and the three wastes is all light than preceding two methods, but the performance of chlorization product is not as solution method.Up to now, do not see the report that useful solid phase method prepares polyolefine chloride coatings as yet.Therefore, if solid phase method has breakthrough on product performance, then solid phase method is more satisfactory method.Purpose of the present invention will address this problem exactly.
The chlorinatedpolyolefins that is used for coating will be soluble in the organic solvent, and the film forming matter content of solution is advisable with＞12%, and viscosity will be suitable for the construction needs.The test back finds that the general commercially available polyethylene product that chlorination gets as raw material does not all meet above-mentioned requirements.This patent through using as chlorizated raw material after the degradation treatment, has not only reduced its molecular weight through pretreated polyethylene with commercially available polyethylene, and studies have shown that through infrared absorption spectrum also to have introduced oxy radical on the sub polyethylene subchain.With the solution that the chlorizate of degrading polyethylene is made into, its coating adhesion is significantly improved.But it is quite difficult that such raw material carries out the solid-phase chlorination reaction, because chlorination reaction is a strong exothermic reaction, is easy to owing to the accumulation of heat material bonding phenomenon take place, and causes reaction to proceed down.The present invention has selected inert filler for use after exploring, for example the compounds of titanium dioxide, talcum powder, carbon black and white carbon black is as separant.Chemical reaction does not take place in this class separant in chlorination reaction process, adverse influence can not take place to the paint film property of chlorizate yet.In addition, when carrying out poly chlorination reaction, must improve temperature of reaction as far as possible, so that the chlorine atom of introducing on sub polyethylene subchain distribution is more even, the polyethylene crystalline fracture must compare thoroughly, thereby the chlorinatedpolyethylene of preparation can satisfy the each side requirement of using as coating.The present invention has realized that with the give phase target of solid phase method chlorinatedpolyethylene as coating, having solved has problem to be solved in the existing technology.
The present invention has following several characteristics: one, the present invention adopts the method for degradation treatment to make molecular weight of polyethylene by original 1～2 * 10
5Reduce to 1.0～2.5 * 10
4, corresponding melting index is/10 minutes (pressure 0.46kg/cm of 5～15 grams
2, 190 ℃ of temperature); Its two, be to explore separant efficiently, this class separant is the inert substance that chemical reaction can not take place in chlorination reaction process, as titanium dioxide and so on inorganic oxygen-containing compound and carbon black etc.This class material grains is trickle, and surface-area is bigger, can prevent effectively that material from boning under heating.Its three, the temperature of chlorination reaction can reach 110～150 ℃.The chlorinity of chlorizate can reach 55～70%.The resulting chlorinatedpolyethylene of method according to the present invention's proposition, has the good solubility energy during as coating, resin content reaches at 20% o'clock, the viscosity that is coated with 25 ℃ in No. 4 cups is about 30 seconds, the sticking power of filming after tested can reach primary standard (drawing the circle method), in addition, also has good snappiness, shock strength and hardness.Show suitable signal paint as rust-inhibiting paint, anticorrosive coating, antifouling paint and airport, highway etc. through little sample testing.
Embodiments of the invention:
Example 1:
Chlorination reactor is the 500ml there-necked flask, has equipped effective agitator on it, during reaction must constantly stir.Add pulverous polyethylene of 100g and 10 gram white carbon blacks in the reactor, the back that stirs feeds chlorine, after the air in the reactive system is replaced, can heat up and react.Constantly emit byproduct hydrogen chloride in the reaction process, the discharge that mixes of it and excessive chlorine, the available absorption bottle that contains water comes absorbing hydrogen chloride, and chlorine remaining in the tail gas then absorbs with alkali, or is circulated back in the reaction system and is used.
When reacting initial, temperature of reaction is decided to be 80 ℃, and along with the carrying out of reaction, temperature of reaction improves thereupon, and final stage is raised to 140 ℃.Stopped reaction when cl content reaches 60%.
Reaction result obtains loose pulverulent solids, is soluble in toluene-acetone-n-butyl acetate mixed solvent, and the solution of solid content 20% is coated with-4 glasss of flushing times in the time of 25 ℃ be 29 seconds.Its coating is tested by coating testing standard promulgated by the ministries or commissions of the Central Government, and shock strength is 45 kilograms centimetres, and snappiness is that the diameter of axle passes through for 5 millimeters, and hardness is 0.683(t/to), sticking power is one-level.
Example 2～5
The device of test is identical with example 1 with step, and different is that the chlorination degree is different.The performance that table 1 is listed for filming behind the chlorizate wiring solution-forming of different chlorinity:
Table 1 chlorinity and the mechanical property of filming
Instance number chlorinity (%) sticking power (level) shock strength snappiness hardness
（kg·cm） （mm） （t/to）
2 45 1 50 1 0.465
3 52 1 45 2 0.580
4 58 1 45 3 0.743
1 60 1 45 5 0.683
5 62 1 25 10 0.729
Table 2 has been listed with acidproof, alkaline-resisting, the salt water resistance of filming of making of example 3 samples and oil resisting test result.
The chemical resistance that table 2 typical case films
The variation of filming of chemical reagent soak time
Sulfuric acid (75%) 60 day is non-foaming, do not come off, nondiscoloration
Sodium hydroxide (10%) 15 day is non-foaming, do not come off, variable color
Salt solution (3%) 30 day is non-foaming, do not come off, variable color
Gasoline 15 days is non-foaming, do not come off, be not clamminess
Example 6～8
The device of test is identical with example 1 with step, and different is that raw material specification is different, and the film performance of institute's wiring solution-forming is as shown in table 3
Table 3 raw material specification and film performance relation
The instance number melting index
*Cl content viscosity sticking power shock strength snappiness hardness
(restraining/10 minutes) (%) (second) (level) (kgcm) (mm) (t/to)
6 4.48 59 46 2 40 1 0.559
7 10.1 55 32 1 50 2 0.579
8 15.2 60 29 1 50 2 0.683
* pressure 0.46kg/cm
2, 190 ℃ of temperature
Claims (8)
1, a kind of preparation method who is suitable for the chlorinatedpolyolefins that coating uses, it relates to the gas-solid phase reaction of polyolefine and chlorine, it is characterized in that adopting through the pretreated polyethylene powders of degraded as chlorizated raw material, in the presence of separant, be close to or higher than the chlorinatedpolyolefins that chlorination under the polyethylene fusing point prepares high chlorine contents.
2, the chlorizated raw material of being mentioned in the claim 1 is a powdery polyethylene, comprises the homopolymer and the interpolymer of ethene.The granularity that it is characterized in that polymkeric substance is≤powder of 1mm.
3, the pre-treatment of being mentioned in the claim 1 is characterized in that comprising the process of thermal destruction, thermooxidative degradation, photodegradation and photo-oxidative degradation, and the molecular weight that makes polyethylene powders is by original 1～2 * 10
5Reduce to 1.0～2.5 * 10
4, do not contain or contain oxide group on the pretreated sub polyethylene subchain.
4, the separant of indication can prevent material agglutinating pressed powder for some in the claim 1 in reaction process.It is characterized in that this class powder is difficult for and chlorine or hydrogenchloride generation chemical reaction.This class separant such as titanium dioxide, carbon black, white carbon black and talcum powder etc.
5, the temperature of reaction of indication in claim 1 is characterized in that referring in the presence of the separant related in claim 4, allows under 120～150 ℃ of temperature, to carry out chlorination reaction, and the unlikely reaction mass bonding phenomenon that causes.
6, related its feature of separant both can be that a kind of separant uses separately in claim 4, also can mix use for multiple separant.Its consumption is 0.5～20% of a polyethylene weight.
7, related temperature of reaction in claim 4, both it is characterized in that in reaction process can temperature-gradient method to the temperature of reaction of regulation, also can heat up continuously, reach the temperature of reaction of regulation at last.
8, the chlorinatedpolyolefins of the high chlorine contents of indication in claim 1 is characterized in that referring to that the chlorinity that can meet the coating requirement reaches 45～70% chlorinatedpolyolefins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86106365 CN86106365A (en) | 1986-09-12 | 1986-09-12 | The preparation method of polyolefine chloride coatings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86106365 CN86106365A (en) | 1986-09-12 | 1986-09-12 | The preparation method of polyolefine chloride coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86106365A true CN86106365A (en) | 1988-03-23 |
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ID=4803170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86106365 Pending CN86106365A (en) | 1986-09-12 | 1986-09-12 | The preparation method of polyolefine chloride coatings |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041940C (en) * | 1994-12-28 | 1999-02-03 | 青岛昌泰祥工贸有限公司 | Preparation method of high chlorinated polyethylene |
| CN1045097C (en) * | 1995-03-22 | 1999-09-15 | 武汉市高校新技术研究所 | Special antirust anticorrosive paint HCPE |
| CN107141381A (en) * | 2017-05-16 | 2017-09-08 | 北京清诚华宇科技有限公司 | The method that gas solid method multi component particle fluid bed prepares haloflex |
| CN108602911A (en) * | 2016-02-25 | 2018-09-28 | 株式会社钟化 | The manufacturing method of chlorinated vinyl chloride-based resin |
| CN109111534A (en) * | 2018-06-26 | 2019-01-01 | 青岛科技大学 | A kind of method that temperature-gradient method prepares haloflex |
-
1986
- 1986-09-12 CN CN 86106365 patent/CN86106365A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041940C (en) * | 1994-12-28 | 1999-02-03 | 青岛昌泰祥工贸有限公司 | Preparation method of high chlorinated polyethylene |
| CN1045097C (en) * | 1995-03-22 | 1999-09-15 | 武汉市高校新技术研究所 | Special antirust anticorrosive paint HCPE |
| CN108602911A (en) * | 2016-02-25 | 2018-09-28 | 株式会社钟化 | The manufacturing method of chlorinated vinyl chloride-based resin |
| CN107141381A (en) * | 2017-05-16 | 2017-09-08 | 北京清诚华宇科技有限公司 | The method that gas solid method multi component particle fluid bed prepares haloflex |
| CN109111534A (en) * | 2018-06-26 | 2019-01-01 | 青岛科技大学 | A kind of method that temperature-gradient method prepares haloflex |
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