CN109251444A - Plasticizer for polyvinyl chloride and preparation method thereof - Google Patents
Plasticizer for polyvinyl chloride and preparation method thereof Download PDFInfo
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- CN109251444A CN109251444A CN201811317530.3A CN201811317530A CN109251444A CN 109251444 A CN109251444 A CN 109251444A CN 201811317530 A CN201811317530 A CN 201811317530A CN 109251444 A CN109251444 A CN 109251444A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The present invention provides a kind of plasticizer for polyvinyl chloride and preparation method thereof, comprising the following steps: 1) preparation of modified material: after castor oil, glacial acetic acid and phosphoric acid are mixed, mixed liquor X1 is made；Hydrogen peroxide is added dropwise into mixed liquor X1, and reacts 4-6h under conditions of being 50-60 DEG C in temperature, mixed liquor X2 is made；Mixed liquor X2 is evaporated under reduced pressure, modified material is obtained；2) preparation of intermediate: modified material obtained in step 1) and DOPO are placed under conditions of temperature is 150-180 DEG C after react 5-8h, vacuum distillation, obtained intermediate；3) preparation of plasticizer for polyvinyl chloride: intermediate and acetic anhydride are placed under conditions of temperature is 130-150 DEG C after mixing 1-3h, plasticizer for polyvinyl chloride is made in vacuum distillation.Realize that environmentally protective, flame retardant property is good, and tensile property still good effect.
Description
Technical field
The present invention relates to plasticizer materials fields, particularly, are related to a kind of plasticizer for polyvinyl chloride and preparation method thereof.
Background technique
Plasticizer can change the important additives of the mechanical performance of plastic or other material as one kind, be widely used in
In production and life all parts.Meanwhile increasing rapidly with China's plastic products, the demand of plasticizer also increase increasingly
It is long.In plastic products, polyvinyl chloride rubber and plastic products are even more to be widely used, and can be used in polyvinyl chloride material
Plasticizer kind it is also more, for example, the maximum plasticizer of accounting is phthalate.But due to O-phthalic
Acid ester type plasticizer can the multiple support channels such as oral, respiratory tract enter human body, and there is biggish toxicity to body, therefore recognized
To be a kind of environment incretion interference factor, especially for children and pregnant woman, endanger even more self-evident.
Although some introductions about green, environmentally friendly, low toxicity plasticizer are provided in the prior art, for example, vegetable oil
Base plasticizer, it is still, poor so as to cause flame retardant property so that it is compared with easy firing often because of vegetable oil reason itself, to making
With bringing certain hidden danger.
Summary of the invention
It is an object of that present invention to provide a kind of plasticizer for polyvinyl chloride and preparation method thereof, past with the plasticizer for solving traditional
Toward not degradable, harm to the human body is big, and environmentally friendly degree is poor, and general degradable plant oil base class plasticizer then Yin Qiben
Body performance causes plastic product poor flame retardant properties compared with easy firing when in use, to using the problem of bringing hidden danger.
To achieve the above object, the present invention provides a kind of preparation methods of plasticizer for polyvinyl chloride, wherein including following
Step:
1) after castor oil, glacial acetic acid and phosphoric acid are mixed, mixed liquor X1 the preparation of modified material: is made；To mixed liquor X1
Middle dropwise addition hydrogen peroxide, and 4-6h is reacted under conditions of being 50-60 DEG C in temperature, mixed liquor X2 is made；Mixed liquor X2 is depressurized and is steamed
It evaporates, obtains modified material；
2) modified material obtained in step 1) and DOPO the preparation of intermediate: are placed in the item that temperature is 150-180 DEG C
After reacting 5-8h under part, intermediate is made in vacuum distillation；
3) preparation of plasticizer for polyvinyl chloride: intermediate and acetic anhydride are placed under conditions of temperature is 130-150 DEG C and mixed
After closing 1-3h, plasticizer for polyvinyl chloride is made in vacuum distillation.
Preferably, relative to the castor oil of 100 parts by weight, the dosage of glacial acetic acid is 10-20 weight in step 1)
Part, the dosage of phosphoric acid is 0.5-2 parts by weight, and the dosage of hydrogen peroxide is 50-100 parts by weight.
Preferably, the time for adding of hydrogen peroxide is 20-25min, and drop rate is not less than 50 drops/min.
Preferably, reaction process is to be placed under stirring condition to react, and stirring rate is 300- in step 1)
500r/min。
Preferably, relative to the modified material of 100 parts by weight, the dosage of DOPO is 30-50 weight in step 2)
Part.
Preferably, further include taking supernatant after the mixture after reaction is stood 36-60h in step 2), and it will be upper
Clear liquid is washed to pH as after 6.5-8, intermediate is made in vacuum distillation.
Preferably, relative to the intermediate of 100 parts by weight, the dosage of acetic anhydride is 60-90 weight in step 3)
Part.
Additionally provide a kind of plasticizer for polyvinyl chloride, wherein the plasticizer for polyvinyl chloride is according to preparation described above
Method is made.
The invention has the following advantages: the present invention using hydrogen peroxide as oxidant, is made using glacial acetic acid/Phosphoric Acid
Castor oil is catalyzed for Oxygen carrying agent, epoxidation reaction is brought it about, synthesizes epoxy castor oil, greatly improve its epoxide number, make
The double bond structure itself contained largely passes through epoxidation reaction and has obtained effective reaction, so that its oxygen index (OI) is improved, into
One step improves its flame retardant property.Further by above-mentioned modified material with certain flame retardant property DOPO under certain condition
Hybrid reaction, so that it in burning and decomposable process, due to itself containing a large amount of ester bond and benzene ring structure, has higher
Stability, meanwhile, because it is with epoxy castor oil structure, in conjunction with active hydrogen in DOPO molecule as reaction center, effective shape
As good carbon forming agent, polyvinyl chloride can be promoted to form fine and close carburization zone in surface in burning, protect lower layer's product,
Also removing hydrogen chloride is further prevented, to effectively avoid generating microcellular structure, and then is more not easy to its burning, more preferably
Play flame retardant effect in ground.Meanwhile hydroxyl and acetic anhydride generation esterification in above-mentioned intermediate, it further reduced intermediate
The degree of branching in molecular structure, and be formed as epoxy construction in conjunction with modified material, it also can preferably reduce the branching of integral material
Degree, by the reduction of the degree of branching, further ensures its plasticizing capacity.Meanwhile whole system to be to be modified castor oil, and
Not degradable material is not added, its safety has been effectively ensured, environmentally friendly degree is also higher.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
The present invention is further detailed explanation below.
Specific embodiment
The embodiment of the present invention is described in detail below, but the present invention can be limited and be covered according to claim
Multitude of different ways implement.
The present invention provides a kind of preparation methods of plasticizer for polyvinyl chloride, wherein the following steps are included:
1) after castor oil, glacial acetic acid and phosphoric acid are mixed, mixed liquor X1 the preparation of modified material: is made；To mixed liquor X1
Middle dropwise addition hydrogen peroxide, and 4-6h is reacted under conditions of being 50-60 DEG C in temperature, mixed liquor X2 is made；Mixed liquor X2 is depressurized and is steamed
It evaporates, obtains modified material；
2) modified material obtained in step 1) and DOPO the preparation of intermediate: are placed in the item that temperature is 150-180 DEG C
After reacting 5-8h under part, intermediate is made in vacuum distillation；
3) preparation of plasticizer for polyvinyl chloride: intermediate and acetic anhydride are placed under conditions of temperature is 130-150 DEG C and mixed
After closing 1-3h, plasticizer for polyvinyl chloride is made in vacuum distillation.
The invention has the following advantages: the present invention using hydrogen peroxide as oxidant, is made using glacial acetic acid/Phosphoric Acid
Castor oil is catalyzed for Oxygen carrying agent, epoxidation reaction is brought it about, synthesizes epoxy castor oil, greatly improve its epoxide number, make
The double bond structure itself contained largely passes through epoxidation reaction and has obtained effective reaction, so that its oxygen index (OI) is improved, into
One step improves its flame retardant property.Further by above-mentioned modified material with certain flame retardant property DOPO under certain condition
Hybrid reaction, so that it in burning and decomposable process, due to itself containing a large amount of ester bond and benzene ring structure, has higher
Stability, meanwhile, because it is with epoxy castor oil structure, in conjunction with active hydrogen in DOPO molecule as reaction center, effective shape
As good carbon forming agent, polyvinyl chloride can be promoted to form fine and close carburization zone in surface in burning, protect lower layer's product,
Also removing hydrogen chloride is further prevented, to effectively avoid generating microcellular structure, and then is more not easy to its burning, more preferably
Play flame retardant effect in ground.Meanwhile hydroxyl and acetic anhydride generation esterification in above-mentioned intermediate, it further reduced intermediate
The degree of branching in molecular structure, and be formed as epoxy construction in conjunction with modified material, it also can preferably reduce the branching of integral material
Degree, by the reduction of the degree of branching, further ensures its plasticizing capacity.Meanwhile whole system to be to be modified castor oil, and
Not degradable material is not added, its safety has been effectively ensured, environmentally friendly degree is also higher.
The dosage of above-mentioned raw materials can be selected in a wide range, certainly, in a preferred embodiment, be
Further such that double bond fracture rate is higher in castor oil, effectively it is modified, in step 1), relative to 100 parts by weight
Castor oil, the dosage of glacial acetic acid is 10-20 parts by weight, and the dosage of phosphoric acid is 0.5-2 parts by weight, and the dosage of hydrogen peroxide is 50-
100 parts by weight.
In one kind more preferably embodiment, the time for adding of hydrogen peroxide is 20-25min, and drop rate is not less than
50 drops/min.Further, the drop rate during being added dropwise by control hydrogen peroxide, makes it during the reaction, can make
Hydrogen peroxide is sufficiently combined with castor oil, and promotees to bring it about epoxidation reaction, and the conversion ratio of oxidation process is improved with this, is improved
The yield of modified material, and the reaction time is further controlled, stabilized hydrogen peroxide can be effectively controlled, further avoids reacting
Hydrogen peroxide is influenced by illumination, the dust etc. in environment in the process.
In another preferred embodiment, in order to enable can effectively be contacted between each raw material, reaction efficiency, step are improved
It is rapid 1) in, reaction process is to be placed under stirring condition and react, and stirring rate is 300-500r/min.
Similarly, in a kind of preferred embodiment, in step 2), relative to the modified material of 100 parts by weight, DOPO's
Dosage is 30-50 parts by weight.
In further preferred embodiment, in order to preferably remove the impurity in reaction process, the increasing of plasticizer is improved
Plasticity energy and flame retardant property further include that supernatant is taken after the mixture after reaction to be stood to 36-60h in step 2), and by supernatant
Liquid is washed to pH as after 6.5-8, intermediate is made in vacuum distillation.
In a kind of preferred embodiment, in step 3), relative to the intermediate of 100 parts by weight, the dosage of acetic anhydride is
60-90 parts by weight.
Additionally provide a kind of plasticizer for polyvinyl chloride, wherein the plasticizer for polyvinyl chloride is according to preparation described above
Method is made.
It is further elaborated below by way of specific embodiment.
Embodiment 1
1) after mixing the phosphoric acid of the castor oil of 100g, the glacial acetic acid of 10g and 0.5g, mixed liquor X1 is made；To mixed liquor
The hydrogen peroxide (dripping in 20min) of 50g is added dropwise in X1, and is stirred under conditions of being 50 DEG C in temperature with the rate of 300r/min
4h is reacted, mixed liquor X2 is made；Mixed liquor X2 is evaporated under reduced pressure, modified material is obtained；
2) modified material of 100g is placed under conditions of temperature is 150 DEG C with the DOPO of 30g after reacting 5h after standing 36h
Supernatant is taken, and it is 6.5 that supernatant, which is washed to pH, is then evaporated under reduced pressure, intermediate is made；
3) acetic anhydride of the intermediate of 100g and 60g is placed under conditions of temperature is 130 DEG C after mixing 1h, decompression is steamed
It evaporates, plasticizer for polyvinyl chloride A1 is made.
Embodiment 2
1) after mixing the phosphoric acid of the castor oil of 100g, the glacial acetic acid of 20g and 2g, mixed liquor X1 is made；To mixed liquor X1
The middle hydrogen peroxide (being dripped in 20min) that 100g is added dropwise, and stirred under conditions of being 60 DEG C in temperature with the rate of 500r/min
6h is reacted, mixed liquor X2 is made；Mixed liquor X2 is evaporated under reduced pressure, modified material is obtained；
2) modified material of 100g is placed under conditions of temperature is 180 DEG C with the DOPO of 50g after reacting 8h after standing 60h
Supernatant is taken, and it is 8 that supernatant, which is washed to pH, is then evaporated under reduced pressure, intermediate is made；
3) acetic anhydride of the intermediate of 100g and 90g is placed under conditions of temperature is 150 DEG C after mixing 3h, decompression is steamed
It evaporates, plasticizer for polyvinyl chloride A2 is made.
Embodiment 3
1) after mixing the phosphoric acid of the castor oil of 100g, the glacial acetic acid of 15g and 1g, mixed liquor X1 is made；To mixed liquor X1
The middle hydrogen peroxide (being dripped in 20min) that 80g is added dropwise, and stirred under conditions of being 60 DEG C in temperature with the rate of 500r/min anti-
4h is answered, mixed liquor X2 is made；Mixed liquor X2 is evaporated under reduced pressure, modified material is obtained；
2) modified material of 60g is placed under conditions of temperature is 160 DEG C with the DOPO of 15g after reacting 6h after standing 48h
Supernatant is taken, and it is 7.5 that supernatant, which is washed to pH, is then evaporated under reduced pressure, intermediate is made；
3) acetic anhydride of the intermediate of 40g and 30g is placed under conditions of temperature is 140 DEG C after mixing 2h, vacuum distillation,
Plasticizer for polyvinyl chloride A3 is made.
Embodiment 4
If prepared by the method for embodiment 1, unlike, the dosage of glacial acetic acid is 5g, and the dosage of hydrogen peroxide is 30g,
Plasticizer for polyvinyl chloride A4 is made.
Embodiment 5
If prepared by the method for embodiment 2, unlike, the dosage of DOPO is 20g, and plasticizer for polyvinyl chloride is made
A5。
Embodiment 6
If prepared by the method for embodiment 3, unlike, directly the mixture after reaction is depressurized in step 2) and is steamed
It evaporates, plasticizer for polyvinyl chloride A6 is made.
Embodiment 7
If prepared by the method for embodiment 3, unlike, the dosage of acetic anhydride is 30 parts by weight, and polyvinyl chloride is made
Plasticizer A 7.
Embodiment 8
If prepared by the method for embodiment 3, unlike, drop rate is that (time for adding is controlled in 1h 20 drops/min
Left and right), plasticizer for polyvinyl chloride A8 is made.
Comparative example 1
If prepared by the method for embodiment 1, unlike, without step 1), castor oil is directly substituted into modified material
Plasticizer for polyvinyl chloride B1 is made in material.
Comparative example 2
If prepared by the method for embodiment 2, unlike, without step 2), directly by modified material and acetic anhydride
Plasticizer for polyvinyl chloride B2 is made in mixing.
Comparative example 3
If prepared by the method for embodiment 3, unlike, without step 3), directly using intermediate as polychlorostyrene second
Alkene plasticizer B3.
Comparative example 4
Commercially available dioctyl phthalate B4.
Comparative example 5
Commercially available dioctyl phthalate and DOPO are according to the mixed mixture B5 of 1:0.1.
Application examples
After above-mentioned A1-A7 and B1-B4 are mixed with polyvinyl chloride according to the ratio that parts by weight are 4:10 respectively, then thereto
Be added 70 parts by weight tetrahydrofuran be placed on 60 DEG C under conditions of be stirred 1h, then pour into and dry 48h in surface plate, then
30min is dried with 60 DEG C of condition, obtains plastized polyvinyl chloride.
Detection data
By above-mentioned plastized polyvinyl chloride using thermogravimetric analyzer detection thermal degradation temperature and Residual carbon, according to GB/T2406.1
Using limit oxygen index analyzer detectable limit oxygen index (OI), data are as shown in table 1.Its fracture is detected according to GB/T1040.1 simultaneously
Elongation and tensile strength, data are as shown in table 2.
Table 1
| Number | Degradation temperature (DEG C) | Residual carbon (%) | Limit oxygen index (%) |
| A1 | 315.6 | 15.23 | 41.2 |
| A2 | 305.8 | 14.89 | 42.8 |
| A3 | 321.1 | 15.28 | 42.5 |
| A4 | 272.8 | 11.35 | 30.6 |
| A5 | 293.6 | 13.16 | 38.7 |
| A6 | 285.9 | 12.89 | 39.2 |
| A7 | 298.6 | 13.10 | 39.4 |
| A8 | 296.8 | 13.15 | 38.9 |
| B1 | 251.3 | 7.12 | 22.6 |
| B2 | 289.6 | 13.15 | 37.8 |
| B3 | 268.9 | 11.6 | 31.2 |
| B4 | 248.7 | 6.31 | 21.6 |
| B5 | 278.9 | 10.96 | 29.6 |
Table 2
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of plasticizer for polyvinyl chloride, which comprises the following steps:
1) after castor oil, glacial acetic acid and phosphoric acid are mixed, mixed liquor X1 the preparation of modified material: is made；It is dripped into mixed liquor X1
Add hydrogen peroxide, and react 4-6h under conditions of being 50-60 DEG C in temperature, mixed liquor X2 is made；Mixed liquor X2 is evaporated under reduced pressure, is obtained
To modified material；
2) preparation of intermediate: modified material obtained in step 1) and DOPO are placed under conditions of temperature is 150-180 DEG C
After reacting 5-8h, intermediate is made in vacuum distillation；
3) preparation of plasticizer for polyvinyl chloride: intermediate and acetic anhydride are placed under conditions of temperature is 130-150 DEG C and mix 1-
After 3h, plasticizer for polyvinyl chloride is made in vacuum distillation.
2. preparation method according to claim 1, which is characterized in that the castor-oil plant in step 1), relative to 100 parts by weight
Oil, the dosage of glacial acetic acid are 10-20 parts by weight, and the dosage of phosphoric acid is 0.5-2 parts by weight, and the dosage of hydrogen peroxide is 50-100 weight
Part.
3. preparation method according to claim 1 or 2, which is characterized in that the time for adding of hydrogen peroxide is 20-25min, and
Drop rate is not less than 50 drops/min.
4. preparation method according to claim 1 or 2, which is characterized in that in step 1), reaction process is to be placed in stirring bar
It is reacted under part, and stirring rate is 300-500r/min.
5. preparation method according to claim 1, which is characterized in that the modification material in step 2), relative to 100 parts by weight
Material, the dosage of DOPO are 30-50 parts by weight.
6. preparation method according to claim 1 or 5, which is characterized in that further include the mixing after reacting in step 2)
Object takes supernatant after standing 36-60h, and supernatant is washed to pH as after 6.5-8, intermediate is made in vacuum distillation.
7. preparation method according to claim 1, which is characterized in that the centre in step 3), relative to 100 parts by weight
Body, the dosage of acetic anhydride are 60-90 parts by weight.
8. a kind of plasticizer for polyvinyl chloride, which is characterized in that the plasticizer for polyvinyl chloride is any one in -7 according to claim 1
Preparation method described in is made.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811317530.3A CN109251444A (en) | 2018-11-07 | 2018-11-07 | Plasticizer for polyvinyl chloride and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811317530.3A CN109251444A (en) | 2018-11-07 | 2018-11-07 | Plasticizer for polyvinyl chloride and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082769A (en) * | 2023-03-22 | 2023-05-09 | 甘肃金川恒信高分子科技有限公司 | Environment-friendly polyvinyl chloride composite material and preparation method thereof |
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| CN101343380A (en) * | 2008-09-02 | 2009-01-14 | 山东蓝帆塑胶股份有限公司 | Method for preparing elasticizer |
| CN108410092A (en) * | 2018-04-10 | 2018-08-17 | 朱文杰 | A kind of preparation method of polyvinyl-chloride use plasticizer |
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2018
- 2018-11-07 CN CN201811317530.3A patent/CN109251444A/en not_active Withdrawn
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| CN101343380A (en) * | 2008-09-02 | 2009-01-14 | 山东蓝帆塑胶股份有限公司 | Method for preparing elasticizer |
| CN108410092A (en) * | 2018-04-10 | 2018-08-17 | 朱文杰 | A kind of preparation method of polyvinyl-chloride use plasticizer |
Non-Patent Citations (1)
| Title |
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| 贾普友: "蓖麻油基磷酸酯类阻燃型塑料增塑剂的合成和性能研究", 《中国博士学位论文全文数据库 工程科技I辑（月刊）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082769A (en) * | 2023-03-22 | 2023-05-09 | 甘肃金川恒信高分子科技有限公司 | Environment-friendly polyvinyl chloride composite material and preparation method thereof |
| CN116082769B (en) * | 2023-03-22 | 2023-06-27 | 甘肃金川恒信高分子科技有限公司 | Environment-friendly polyvinyl chloride composite material and preparation method thereof |
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