CN1025788C - Preparation of polyethylene plasticizers from oil and fats of animal or vegetable - Google Patents
Preparation of polyethylene plasticizers from oil and fats of animal or vegetable Download PDFInfo
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- CN1025788C CN1025788C CN 89105249 CN89105249A CN1025788C CN 1025788 C CN1025788 C CN 1025788C CN 89105249 CN89105249 CN 89105249 CN 89105249 A CN89105249 A CN 89105249A CN 1025788 C CN1025788 C CN 1025788C
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- polyvinyl chloride
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Abstract
The present invention relates to a polyvinyl chloride plasticizer prepared from animal and vegetable oil and fat, and a preparation method for the polyvinyl chloride plasticizer, which belongs to the field of macromolecule modification. Chlorination reaction and the addition reaction of hydrogen chloride are carried out on animal and vegetable oil and fat, and the polyvinyl chloride plasticizer, namely chloro-oil and fat is obtained, wherein the polyvinyl chloride plasticizer has big molecular weight and high intermiscibility with polyvinyl chloride and is flameproof. A polyvinyl chloride product plasticized by the plasticizer with the addition of other auxiliary agents can be used for a long term at a high temperature and can keep the physical and mechanical properties. The present invention has the advantages of simple technology, easy obtainment of raw materials and no three waste pollution and is capable of overcoming the disadvantages of tension in supply and poor performance of the existing polyvinyl chloride plasticizer.
Description
The invention provides a kind of plasticizer for polyvinyl chloride, particularly a kind of plasticizer for polyvinyl chloride of using the preparation of animal and plant grease and preparation method thereof, it belongs to the polymer modification field.
In the forming process and application process of macromolecular material,, just must add a certain amount of softening agent therein in order to regulate its physics, mechanical property and processing characteristics to make it to be satisfied with the needs of different purposes.Some softening agent of having widely applied at present is because the limitation of its performance and raw material sources still can not satisfy industrial needs fully.Phthalate for example, although itself and polyvinyl chloride have good intermiscibility, polyvinyl chloride had good plasticization effect, it is present general polyvinyl chloride main plasticizer, but this softening agent has the lower characteristics of molecular weight, thereby after meeting heat, easily take place softening with its plastifying polrvinyl chloride product, and this softening agent also has certain toxicity, thereby can not use in the wrapping material of contact food, moreover this softening agent also has shortcomings such as relatively poor and raw material (phthalic anhydride etc.) shortage of flame resistivity.Again for example: another kind of polyester plasticizer is arranged, though its molecular weight is higher, also can play good plasticization effect to polyvinyl chloride, but this softening agent when synthetic complex process (its technological process of production will be passed through: operations such as esterification, neutralization, dealcoholysis, distillation, polymerization, decolouring, press filtration), also relatively poor with its plastifying polrvinyl chloride product flame resistivity.Also has a kind of epoxy grease plasticizer with higher molecular weight, though it is nontoxic, low-temperature performance is good, but the intermiscibility of this softening agent and polyvinyl chloride is relatively poor, so that but addition is very little in goods, can not use as primary plasticizer, can only in most of prescriptions, make extender plasticizer or use as stablizer.Although its main raw material source of this epoxy grease plasticizer is abundant, to expend a considerable amount of peroxidation formic acid or peroxidation acetate when it is synthetic, its aftertreatment technology is also complicated.The flame resistivity of this softening agent is also very poor, and about being raw material with animal and plant sky fuel oil fat, the technical scheme for preparing plasticizer for polyvinyl chloride by chlorination reaction is not seen bibliographical information both at home and abroad as yet at present.
The objective of the invention is: provide a kind of raw material sources to enrich, preparation technology's flow process is simple, and production unit is less, the preparation method of the lower plasticizer for polyvinyl chloride that consumes energy.This softening agent has higher molecular weight, and flame resistivity has good plasticization effect to polyvinyl chloride preferably.Make polrvinyl chloride product with such softening agent, can at high temperature keep good physics, mechanical property and processing characteristics, thereby reach the purpose of as required polyvinyl chloride being carried out plasticization and modification.
Solution of the present invention is: with animal and plant grease and chlorine as the main raw material of synthetic softening agent, utilize chlorination reaction and obtain to be called the greasy reaction product of chloro, be equipped with epoxy grease again, the two is combined into the softening agent that is used for polyvinyl chloride.The quality index of this softening agent is:
Proportion (50 ℃): 0.95～1.25
Chlorinity (weight percent of chlorine): 0.5～45%
Acid number, milligram potassium hydroxide/gram :≤1.0～1.5
Heat decomposition temperature ℃: 〉=160 ℃
The preparation method of this softening agent is: mainly by having the triglyceride structure:
[R wherein
1, R
2And R
3Can be identical alkyl molecular chain, also can be different alkyl molecular chains, and they are to contain
CH
2)
n(n 〉=3
Chain link or contain
CH
2-CH=CH-CH
2 
nThe chain link of (n 〉=0)] animal and plant grease and chlorine and hydrogen chloride gas chlorination and the hydrogenchloride addition reaction carried out.Such animal and plant grease can elder generation and chlorine reaction
The reaction conditions of above-mentioned all reactions is:
A, temperature of reaction: 0～200 ℃
B, reaction initiator: initiator (Diisopropyl azodicarboxylate) consumption: 0～5%(refers to that initiator weight accounts for the per-cent of grease charging capacity);
C, reaction end: when the proportion (50 ℃) of reaction product when being 0.95～1.25, stopped reaction.
When this temperature of reaction surpassed 200 ℃, thermolysis easily took place in reaction product, so temperature control should rather be hanged down not high.If when wanting accelerated reaction, can adopt the method for UV-irradiation, begin to shine during usually from the feeding chlorine of reaction and get final product.When the ratio of reaction product weighs to 0.95～1.25 the time, the molecular weight of reaction product just has been enough to greatly.At this moment,, thereby improved the molecular weight of product because the chlorine atom replaces hydrogen atom and addition chlorine atom and the hydrogen atom at two keys, also improved simultaneously this product flame resistivity and with the polyvinyl chloride intermiscibility.Above-mentioned all reactions can be adjusted to the numerical value identical with the solubility parameter of polyvinyl chloride with the solubility parameter of reaction product by the control level of response, make the chloro grease as primary plasticizer have good plasticization effect to the polyvinyl chloride plastic material products, the reactions steps of this softening agent is:
A, preheating reactor at first make temperature reach 0～140 ℃;
B, feed intake that (the animal and plant grease: these greases are lard, butter, sheep oil, Oleum Gossypii semen, soybean oil, Viscotrol C, the peanut oil that mainly contains the triglyceride structure.When feeding intake, during available above-mentioned all kinds of greasy several greasy mixing, also can be that wherein a certain grease uses separately.) after, when temperature of charge reaches 0～140 ℃, begin to feed chlorine, and heat up gradually, and remain under a certain temperature in 0～200 ℃ of scope (according to circumstances) and carry out chlorination reaction;
C, reaction end gas absorb with alkali lye;
D, reaction end grasp and exist: when the proportion of reaction product reaches 0.95～1.25, get final product stopped reaction, stop to feed chlorine and use bubbling air or nitrogen instead to blow out the chlorine-containing gas in the reaction product.
E, acid number and the further plasticization effect that improves the softening agent of this primary plasticizer in order to reduce reaction product, can be equipped with epoxy grease, its consumption is that 0～50%(finger ring oxygen grease accounts for the greasy weight percent of chloro), be equipped with stirring again, it is mixed, promptly get plasticizer for polyvinyl chloride of the present invention.
Use softening agent of the present invention, can make polyvinyl chloride life-time service and keep its physical and mechanical properties at high temperature, and flame resistivity is arranged, this softening agent also has higher processing stability.Just can find out the premium properties of this softening agent by the test report in the following examples.This softening agent has that raw material sources are extensive, and manufacturing process is simple, three-waste free pollution, the advantage of product performance good (flame resistivity height, good electric property).
Several example of the present invention is as described below:
Example one
Earlier the 0.5m of agitator is being housed
3The chuck of glassed steel reaction vessels in feed warm water with control reaction temperature.In reactor, drop into the 200kg Oleum Gossypii semen, begin to feed chlorine when being warming up to 40 ℃, and when being warming up to 70 ℃ gradually, remaining on and carry out chlorination and hydrogenchloride addition reaction under this temperature.Unreacted a small amount of tail gas Ca(OH)
2The aqueous solution absorbs, and reacts after 5 hours, the stopped reaction when ratio that records reaction product weighs 1.10 left and right sides.Be blown into air to remove unreacted chlorine and hydrogenchloride, add 10 kilograms of epoxy Oleum Gossypii semens (oxirane value 〉=3.4%) at last, stir and open bottom valve after 30 minutes product is emitted, it is as follows to get product quality indicator after by analysis:
Outward appearance is combined look transparent sticking shape liquid
Molecular weight 1.04 * 10
3～1.15 * 10
3
Acid number, milligram potassium hydroxide/gram 1.0～1.5
Heat decomposition temperature ℃ 〉=160 ℃
Hear rate (160 ℃ * 30 minutes), %0.3
Flash-point (driving ware), ℃ 〉=350 ℃
Proportion (50 ℃) 1.10
Undertaken mixing by following prescription and polyvinyl chloride this product:
100 parts of polyvinyl chloride (PVC) RESINS
38 parts of dioctyl phthalate (DOP)s
22 parts of this products
7 parts of stablizers
10 parts of fillers
Used test conditions is as shown in table 1: (table is seen the literary composition back)
The back test result is listed in table 2 in flakes.The national standard of also having listed sheath level CABLE MATERIALS in the table 2 as a comparison.
Example two
Prescription is as follows when being to mix with polyvinyl chloride with example one difference:
100 parts of polyvinyl chloride (PVC) RESINS
38 parts of dioctyl phthalate (DOP)s
24 parts of this products
7 parts of stablizers
10 parts of fillers
Other is all identical with example one.In flakes, test result is listed in table 2.
Example three
Prescription is as follows when being to mix with polyvinyl chloride with example one difference:
100 parts of polyvinyl chloride (PVC) RESINS
60 parts of this products
7 parts of stablizers
10 parts of fillers
Other is all identical with example one.The back test result is listed in table 2 in flakes.
Example four
Be that with example one difference raw material selects the reactant of 200 kilograms of lards as chlorination reaction for use, the reaction times is 6.5 hours, and recording reactant proportion is 1.15 kilograms, stopped reaction.Prescription was when products therefrom mixed with polyvinyl chloride:
100 parts of polyvinyl chloride (PVC) RESINS
60 parts of this products
7 parts of stablizers
20 parts of fillers
Chlorinatedpolyethylene (Cl%=38%) 5
Other is all identical with example one.The back test result is listed in table 2 in flakes.
By table 2 as seen, all be higher than national standard, can be used for 70 ℃ of higher level sheath CABLE MATERIALS by its every index of this product plastifying polrvinyl chloride product.
Table 1: test conditions
Testing installation specification test technology
160 * 320 millimeters of opening rubber mixing machines 155～165 ℃/5 minutes
25 tons of vulcanizing press QLB-II 350 * 350 * 2 165～170 ℃/14 minutes
Table 2: test result table look-up
Test result
Test subject standard instance 1 example 2 examples 3 examples 4
Tensile strength .MPa 〉=15.0 18.1 17.4 20.0 27.2
Elongation at break .% 〉=180 340 342.4 294.4 245
Aging back draft intensity .MPa 〉=15.0 18.5 17.1 18.8 26.5
The maximum velocity of variation .% of tensile strength ± 20 2.2-1.72-6.0 2.8
Aging back elongation at break .% 〉=180 366 370.4 287.2 261
The maximum velocity of variation .% of elongation at break≤20 7.65 8.18-2.44 6.3
Thermal ageing weightlessness (100 ℃/68 hours), g/m≤23 9.7 8.19 11.89 4.15
Thermal distortion, %≤50 42.9 40.5/34
200 ℃ of heat-stable times, branch 〉=50 80 80 //
Volume specific resistance in the time of 20 ℃, Ω m 〉=1.0 * 1.0
81.6 * 10
101.6 * 10
109.3 * 10
118.6 * 10
11
Breakdown voltage strength kv/mm 〉=18 // 20 21
Claims (6)
1, a kind of method for preparing the softening agent of polyvinyl chloride with the animal and plant grease, it is characterized in that: with animal and plant grease and chlorine, at initiator Diisopropyl azodicarboxylate (consumption: 0～5%), under 0～200 ℃ of condition, react, to the proportion (50 ℃) of reaction product be 0.95～1.25 o'clock stopped reaction.
2, press the method for claim 1, it is characterized in that: these animal and plant greases mainly are lard, butter, sheep oil, Oleum Gossypii semen, soybean oil, Viscotrol C, peanut oil or the Semen Lini oil that contains the triglyceride structure, can be above-mentioned all kinds of greasy certain several greasy mixture when feeding intake, also can be that wherein a certain grease uses separately.
3, by the method for claim 1, it is characterized in that: if when wanting accelerated reaction, can adopt UV-irradiation, begin irradiation during from the feeding chlorine of reaction process, until the reaction end of a period.
4, according to the method for claim 1, it is characterized in that: after feeding intake, the preheating reactor when temperature of charge reaches 0～140 ℃, begins logical chlorine, and heats up gradually.
5, by the method for claim 1, it is characterized in that: after reaching reaction end, stop logical chlorine, blow out chlorine-containing gas in the reaction product with air or chlorine, till the acid number (milligram potassium hydroxide/gram)≤1.0～1.5 of reaction product.
6, by the method for one of claim 1～5, it is characterized in that: after reaction stops, also can adding the epoxy grease blending in reaction product-chloro grease, its consumption is that 0～50%(finger ring oxygen grease accounts for the greasy weight percent of chloro).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105249 CN1025788C (en) | 1989-03-11 | 1989-03-11 | Preparation of polyethylene plasticizers from oil and fats of animal or vegetable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105249 CN1025788C (en) | 1989-03-11 | 1989-03-11 | Preparation of polyethylene plasticizers from oil and fats of animal or vegetable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1045591A CN1045591A (en) | 1990-09-26 |
| CN1025788C true CN1025788C (en) | 1994-08-31 |
Family
ID=4856016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89105249 Expired - Fee Related CN1025788C (en) | 1989-03-11 | 1989-03-11 | Preparation of polyethylene plasticizers from oil and fats of animal or vegetable |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1025788C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338041B (en) * | 2008-04-29 | 2011-04-06 | 夏森林 | PVC environment-protecting asepsis toughening agent |
| CN101343380B (en) * | 2008-09-02 | 2011-06-01 | 山东蓝帆塑胶股份有限公司 | Method for preparing elasticizer |
| CN101367958B (en) * | 2008-09-28 | 2011-06-08 | 华南理工大学 | Environment-friendly polyvinyl chloride elasticizer and method of preparing the same |
| CN103756196A (en) * | 2014-01-20 | 2014-04-30 | 山东岩海建设资源有限公司 | Method for preparing PVC (Polyvinyl Chloride) plasticizer |
| CN105601591A (en) * | 2015-12-24 | 2016-05-25 | 宜兴市顺发化工有限公司 | Modified epoxidized soybean oil and preparation method thereof |
| CN106350216A (en) * | 2016-08-25 | 2017-01-25 | 林群祥 | Chlorinated waste edible oil |
| EP3309198A1 (en) * | 2016-10-11 | 2018-04-18 | Klaus Dahleke KG | Bio-based polymer compositions |
| CN111151199A (en) * | 2020-02-12 | 2020-05-15 | 浙江镇洋发展股份有限公司 | Continuous production device and process of chlorinated fatty acid methyl ester |
| CN111925606A (en) * | 2020-07-30 | 2020-11-13 | 宜兴市鸿韵塑料有限公司 | Cold-resistant flame-retardant PVC cable sheath material |
-
1989
- 1989-03-11 CN CN 89105249 patent/CN1025788C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1045591A (en) | 1990-09-26 |
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