CN1041940C - Preparation method of high chlorinated polyethylene - Google Patents
Preparation method of high chlorinated polyethylene Download PDFInfo
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- CN1041940C CN1041940C CN94113370A CN94113370A CN1041940C CN 1041940 C CN1041940 C CN 1041940C CN 94113370 A CN94113370 A CN 94113370A CN 94113370 A CN94113370 A CN 94113370A CN 1041940 C CN1041940 C CN 1041940C
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- chlorinated polyethylene
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- temperature
- polyethylene
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- 239000004709 Chlorinated polyethylene Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000004698 Polyethylene Substances 0.000 claims abstract description 16
- -1 polyethylene Polymers 0.000 claims abstract description 16
- 229920000573 polyethylene Polymers 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims abstract description 10
- 238000010298 pulverizing process Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000007790 solid phase Substances 0.000 claims description 8
- 239000003849 aromatic solvent Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000011159 matrix material Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a preparing method of high chlorinated polyethylene for coating materials, printing ink and adhesives, which comprises a temperature controlling device and a hydrochloric acid recovering device. The preparing method of high chlorinated polyethylene for coating materials, printing ink and adhesives is characterized in that excessive chlorine gas is supplied to polyethylene powder whose molecular weight is from 30000 to 500000 and particle diameter is less than 1mm in a reactor by three or more times at 70 DEG C to 180 DEG C under the condition of the existence of 0.5 wt% to 4 wt% of antisticking agents for a chlorination reaction of gas and sold phases. Simultaneously, the degradation is carried in the chlorination process; then, the high chlorinated polyethylene whose viscosity is controllable and the content of chlorine is from 65 to 75% is obtained by the steps of pugging and pulverization.
Description
The present invention relates to a kind of coating that is used for, printing ink, tackiness agent belongs to macromolecule modified field with the preparation method of highly-chlorinated polyethylene.
Highly-chlorinated polyethylene has good weather-proof, fire-retardant, performances such as chemicals-resistant can be widely used for coating as matrix material, printing ink, fields such as tackiness agent, yet the highly-chlorinated polyethylene of producing with ordinary method, because of molecular weight bigger, its soltion viscosity that is dissolved in the organic solvent has surpassed coating, printing ink, the service requirements of tackiness agent, thus limited its development and application.
The preparation method of highly-chlorinated polyethylene is that the polyethylene of low-molecular-weight polyethylene of employing or process degradation treatment is a raw material in the prior art, adopts solution method, water phase suspension, and the solid phase method chlorination makes highly-chlorinated polyethylene, but all there is deficiency in these methods.
Ger, cast 116242 (1975) discloses a kind of method that adopts solution method to prepare highly-chlorinated polyethylene, but its defective is to need to consume a large amount of organic solvents, the production cost height, and organic solvent has bigger harm again to people and environment simultaneously.
The flat 2-300510 of JP (1990) discloses a kind of method that adopts water phase suspension to produce highly-chlorinated polyethylene, but because the existence of HCl makes equipment corrosion serious in the system, owing to produce a large amount of low-concentration hcls, make three wastes treatment capacity that cost is improved simultaneously.
CN86106365A (1986) discloses a kind of method that adopts solid phase method to produce highly-chlorinated polyethylene, its concrete grammar for adopt with the polyethylene powders after the degradation treatment in the presence of separant in 120 ℃ of-150 ℃ of chlorinations, but the molecular weight of polyethylene of the pre-degradation treatment of warp that adopts during because of chlorination is lower, its molecular weight is between 10000-25000, so its softening temperature is also lower, its softening temperature is less than 120 ℃.For fast reaction speed, should improve temperature of reaction, as long as temperature of reaction improves, reaction is quickened, the reaction liberated heat can make the local reaction temperature improve again, so circulation causes the final material temperature to be higher than softening point temperature and bonds, product chlorination after the bonding is proceeded, but the heat that reaction generates can't shed, have a strong impact on quality product, the extremely difficult control of its reaction process also very easily bonds even there is a large amount of release agents to exist, the existence of a large amount of release agents simultaneously can seriously influence the use properties of product and removes quite difficulty and make the cost increase.Low because of temperature of reaction simultaneously, the chlorine atom skewness on the carbochain can't dissolve it fully with aromatic solvent merely, and the necessary mixed solvent of using can.
CN85105998A discloses the technology that a kind of stirring-type solid-phase chlorination prepares high chlorinated polymer, temperature of reaction is 80 ℃-130 ℃, wherein the chlorinatedpolyethylene chlorinity only is 57-62%, its product cl content is low, chlorine on the carbochain is former skewness, be not soluble in conventional solvent, can not use, generally be used for PVC and PE modification as matrix material.
CN86100452A discloses a kind of method, adopts the method for non-volatile swelling agent, and temperature of reaction is fixed on 110-150 ℃, its objective is to make product have higher elongation and low modulus, to improve mechanical performance of products.
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art.
The object of the present invention is to provide a kind of production cost low, little to equipment corrosion, three wastes treatment capacity is few, the manageable highly-chlorinated polyethylene preparation method of reaction process.
Of the present inventionly advance a purpose and provide a kind of constant product quality, and meet the highly-chlorinated polyethylene of matrix material service requirements.
The present invention is achieved through the following technical solutions:
A kind of coating that is used for, printing ink, the preparation method of the highly-chlorinated polyethylene of bonding agent, comprise temperature regulating device and salt acid-restoring plant, it is characterized in that in reactor with molecular weight being 30000-500000, the powdery polyethylene of particle diameter＜1mm is in the presence of 0.5%-4% (weight) release agent, between 70 ℃-180 ℃ of temperature, divide and feed excessive chlorine more than three sections or three sections and carry out gas-solid phase chlorination reaction, and in chlorination process, degrade simultaneously, obtain the highly-chlorinated polyethylene of the cl content of may command viscosity through mixing and pulverizing then at 65-75%.
Above-mentioned release agent comprises titanium dioxide, barium sulfate, white carbon black.
When dividing three sections to carry out gas-solid phase chlorination reaction, three sections temperature is respectively 70-120 ℃, and 100-150 ℃, 140-180 ℃, three sections cl contenies are respectively＜and 30%,＜60%, 65-75%.
The present invention has following effect:
1 since the present invention to adopt high-molecular weight powdery polyethylene (30000-500000) be raw material, can under higher temperature, (70-180 ℃) carry out gas-solid phase chlorination reaction and the material bonding does not take place, can make product that solvability is preferably arranged in organic solvent, these solvents comprise aromatic hydrocarbons, the ester class, hydrogenation aromatic hydrocarbons, halohydrocarbon etc., and can at room temperature be dissolved in aromatic hydrocarbons.
2 because the temperature of reaction that the present invention adopts is higher, reaches as high as 180 ℃, has so just improved speed of response, has shortened the reaction times.
3 because the present invention has added the release agent of 0.5-4% (weight) in reaction system, has avoided material to bond because of local superheating so effectively.
4 since the present invention adopted divide more than three sections or three sections and in the presence of excessive chlorine chlorination degrade simultaneously, can reduce the molecular weight of chlorinated polymer so effectively, the soltion viscosity that shows as highly-chlorinated polyethylene is suitable as the matrix material use.
5 owing to be controlled at 140 ℃-180 ℃ in final stage temperature of the present invention, can obtain (6.5-100) * 10 like this
-2The viscosity (20% toluene solution, 25 ℃) that requires arbitrarily between the Pas, and last mixing and pulverization process can make product in every respect performance increase.
6 since HCl and unreacted chlorine that the present invention reacts generation handle through deriving outside the reactor continuously, so do not exist water phase suspension to increase owing to degree of depth chlorination makes the reaction medium concentration of hydrochloric acid like that, so the present invention can not cause the heavy corrosion to equipment.
7 owing to derive continuously the outer gas of reactor and wash with water and remove outside the HCl, recyclable concentration of hydrochloric acid height, but chlorine also retrieval system use, so the present invention has the raw material availability height, three wastes treatment capacity is little, the characteristics that production cost is low.
8 highly-chlorinated polyethylenes that adopt method of the present invention to produce can reach following index:
Cl content 65-75%, viscosity (6.5-100) * 10
-2Optional between the Pas (25 ℃ of 20% toluene solutions), color and luster is less than No. 6 (20% toluene solution, iron cobalt colorimetry), and no insolubles, heat decomposition temperature be greater than 100 ℃, and stability is that 20% toluene solution placement 30 days is not stratified, not gel.Can be used as matrix material and be used for coating, printing ink, tackiness agent etc.; And can replace chlorinated rubber effectively.
Hereinafter, the present invention is described in further detail:
The highly-chlorinated polyethylene of using as matrix material will be soluble in organic solvent, and the viscosity of solution will meet service requirements.Poly chlorination reaction is a strong exothermic reaction, particularly in gas-solid phase chlorination reaction, because the bonding of material easily takes place in the local accumulation of heat, in order to make chlorinatedpolyethylene be soluble in organic solvent, need destroy poly crystallization up hill and dale, the chlorine atom of introducing on its molecular chain is evenly distributed, this just needs the certain reaction temperature, yet temperature of reaction is if surpass poly softening temperature, even there is release agent to exist, the material bonding also very easily takes place, but increase along with chlorinatedpolyethylene content, the corresponding raising of its softening temperature, because can under higher temperature, carry out with the polyethylene chlorination reaction that high softening-point is arranged, reaction process also is easier to control, products obtained therefrom has solubility property good in organic solvent, but has polyethylene than high softening-point, its molecular weight is quite big, corresponding muriatic molecular weight is also quite big, the viscosity of its organic solution should not be used as matrix material, be fit to the highly-chlorinated polyethylene that matrix material is used in order to make, the molecular weight of its finished product is unsuitable excessive, so the present invention adopts following scheme:
In reactor, be 30000-500000 with molecular weight, the powdery polyethylene of particle diameter＜1mm is in the presence of 0.5%-4% (weight) release agent, between 70 ℃-180 ℃ of temperature, divide and feed excessive chlorine more than three sections or three sections and carry out gas-solid phase chlorination reaction, and in chlorination process, degrade simultaneously, obtain the highly-chlorinated polyethylene of the cl content of may command viscosity through mixing and pulverizing then at 65-75%.
Above-mentioned release agent comprises titanium dioxide, barium sulfate, white carbon black.
When dividing three sections reactions, three sections temperature is respectively 70-120 ℃, and 100-150 ℃, 140-180 ℃, three sections cl contenies are respectively＜and 30%,＜60%, 65-75%.
The highly-chlorinated polyethylene that adopts method of the present invention to produce can reach following index:
Cl content 65-75%, viscosity (6.5-100) * 10
-2Optional between the Pas (25 ℃ of 20% toluene solutions), color and luster is less than No. 6 (20% toluene solution, iron cobalt colorimetry), and no insolubles, heat decomposition temperature be greater than 100 ℃, and stability is that 20% toluene solution placement 30 days is not stratified, not gel.Can be used as matrix material and be used for coating, printing ink, sticking platform agent etc.; And can replace chlorinated rubber effectively.
The present invention will be further described below to enumerate embodiment, and the present invention is not limited:
Embodiment 1
Mechanical stirring is being housed, ventpipe, thermometer, (petro-chemical fiber industrial in Liaoyang produces GF7750 to add the 100g powder polyethylene in the 500ml reaction flask of vapor pipe, molecular weight 100000-300000) and the white carbon black of 3g, open to stir and open logical chlorine, the air displacement in the reaction flask is come out, behind the hydrochloric acid absorption bottle of tail gas through having weighing device of discharging, utilize again with alkali absorption or Returning reacting system.
Emptying finishes, and begins to heat up, and begins reaction when temperature rises to 70 ℃, the weightening finish of control hydrochloric acid absorption bottle is before 18g, temperature of reaction is no more than 100 ℃, and the weight along with the hydrochloric acid absorption bottle increases and the raising temperature of reaction later on, is stabilized in 175 ℃ at last, when the material chlorinity reaches 72%, be cooled to 80 ℃, blow off chlorine and HCl in the material, after mixing and pulverization process with air, all be dissolved in aromatic solvent under the product room temperature that obtains, its 20% toluene solution viscosity is 7 * 10
-2Pas (25 ℃).Other performance also touches the mark.
Embodiment 2
Experimental installation and step be with embodiment 1, and different is final reaction temperature-stable is at 150 ℃, and the product chlorinity is 65%, all is dissolved in aromatic solvent under the room temperature, and its 20% toluene solution viscosity is 78 * 10
-2Pas (25 ℃).
Embodiment 3
Experimental installation and step are with embodiment 1, different is that the employing polyethylene is the J-O (molecular weight 100000-500000) of second auxiliary factory, Beijing, the products obtained therefrom chlorinity is 70%, all is dissolved in aromatic solvent under this product room temperature, and its 20% toluene solution viscosity is 25 * 10
-2Pa.s (25 ℃).
Embodiment 4
Experimental installation and step are led to embodiment 1, that different is the J-O (molecular weight is 100000-500000) that adopts polyethylene to produce for second auxiliary factory, Beijing, the final stage temperature of reaction is 150 ℃, the products obtained therefrom chlorinity is 68%, all be dissolved in aromatic solvent under the room temperature, its 20% toluene solution viscosity is 90 * 10
-2Pa.s (25 ℃).
Claims (5)
1. one kind is used for coating, printing ink, the preparation method of the highly-chlorinated polyethylene of tackiness agent, comprise temperature regulating device and salt acid-restoring plant, it is characterized in that in reactor with molecular weight being 30000-500000, the powdery polyethylene of particle diameter＜1mm is in the presence of 0.5%-4% (weight) release agent, between 70 ℃-180 ℃ of temperature, divide and feed excessive chlorine more than three sections or three sections and carry out gas-solid phase chlorination reaction, and in chlorination process, degrade simultaneously, obtain the highly-chlorinated polyethylene of the cl content 65-75% of may command viscosity then through mixing and pulverizing.
2. according to the method for claim 1, it is characterized in that above-mentioned release agent comprises titanium dioxide, barium sulfate, white carbon black.
3. the method according to claim 1 is characterized in that three sections temperature is controlled to be 70-120 ℃ respectively when gas-solid phase chlorination reaction divides three sections to react, 100-150 ℃, and 140-180 ℃, three sections cl content is respectively＜and 30%,＜60%, 65-75%.
4. according to the coating that is used for of the method for claim 1 preparation, printing ink, the highly-chlorinated polyethylene of tackiness agent is characterized in that its cl content 65-75%, its 20% toluene solution in the time of 25 ℃ its viscosity 6.5 * 10
2Pas-100 * 10
2Between the Pas, dissolve in aromatic solvent or aromatic hydrocarbons mixed solvent under the room temperature.
5. according to claim 1 highly-chlorinated polyethylene, it is characterized in that described aromatic solvent comprises: benzene, toluene, dimethylbenzene, high boiling aromatic hydrocarbon solvent etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113370A CN1041940C (en) | 1994-12-28 | 1994-12-28 | Preparation method of high chlorinated polyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113370A CN1041940C (en) | 1994-12-28 | 1994-12-28 | Preparation method of high chlorinated polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125734A CN1125734A (en) | 1996-07-03 |
| CN1041940C true CN1041940C (en) | 1999-02-03 |
Family
ID=5036701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94113370A Expired - Fee Related CN1041940C (en) | 1994-12-28 | 1994-12-28 | Preparation method of high chlorinated polyethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1041940C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698687B (en) * | 2009-11-06 | 2012-05-23 | 潍坊亚星集团有限公司 | Method for preparing high-rigidity chlorinated polyethylene |
| CN105504108B (en) * | 2016-01-05 | 2017-10-31 | 临沂奥星化工有限公司 | A kind of preparation method of highly-chlorinated polyethylene |
| 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 |
| CN109134717B (en) * | 2018-06-26 | 2021-04-16 | 青岛科技大学 | Production process for preparing chlorinated polyethylene by segmented temperature rise solid phase method |
| CN110172111B (en) * | 2019-05-09 | 2022-05-10 | 山东高信化学股份有限公司 | Preparation method of low-temperature-resistant high-chlorinated polyethylene resin for glue |
| CN111995701A (en) * | 2020-09-09 | 2020-11-27 | 安徽华纳化学工业有限公司 | Preparation method of chlorinated polyethylene |
| CN112874101B (en) * | 2021-02-18 | 2022-08-09 | 石家庄康岁商贸有限公司 | Reflective warning tape and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105998A (en) * | 1985-08-07 | 1987-02-25 | 湖北省化学研究所 | The technology of producing chlorinated high polymers by solid phase chlorination under stirring |
| CN86106365A (en) * | 1986-09-12 | 1988-03-23 | 青岛化工学院 | The preparation method of polyolefine chloride coatings |
-
1994
- 1994-12-28 CN CN94113370A patent/CN1041940C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105998A (en) * | 1985-08-07 | 1987-02-25 | 湖北省化学研究所 | The technology of producing chlorinated high polymers by solid phase chlorination under stirring |
| CN86106365A (en) * | 1986-09-12 | 1988-03-23 | 青岛化工学院 | The preparation method of polyolefine chloride coatings |
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| Publication number | Publication date |
|---|---|
| CN1125734A (en) | 1996-07-03 |
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