CN106674398A - Poly(methacrylic acid) phosphate ester and preparation method thereof and aluminum-casting crystallizer mold oil prepared by using poly(methacrylic acid) phosphate ester - Google Patents
Poly(methacrylic acid) phosphate ester and preparation method thereof and aluminum-casting crystallizer mold oil prepared by using poly(methacrylic acid) phosphate ester Download PDFInfo
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- CN106674398A CN106674398A CN201610815870.3A CN201610815870A CN106674398A CN 106674398 A CN106674398 A CN 106674398A CN 201610815870 A CN201610815870 A CN 201610815870A CN 106674398 A CN106674398 A CN 106674398A
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- phosphate ester
- acid
- ester
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- methacrylic acid
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- 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
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention relates to a poly(methacrylic acid) phosphate ester and a preparation method thereof and aluminum-casting crystallizer mold oil prepared by using the poly(methacrylic acid) phosphate ester. Particularly, the invention discloses the poly(methacrylic acid) phosphate ester which is prepared from the following components: methacrylic acid, fatty alcohol, polyhydric alcohol and phosphoric acid; and the ratios of the components are described in the instructions. The invention further discloses a preparation method and application of the poly(methacrylic acid) phosphate ester.
Description
Technical field
The invention belongs to ejection technique field, is related to a kind of polymethylacrylic acid phosphate ester and preparation method thereof and uses the ester
Prepare aluminum casting crystallizer mould oil.
Background technology
The aluminium alloy processing casting demoulding traditionally typically applies one layer of graphited oil in die surface, this processing technique
Have the disadvantage that human cost is high, smear uneven by hand, high temperature smolders serious when casting, mould is impaired big, finished surface flatness
Difference etc..
Many more than due to haveing the shortcomings that, new casting releasing process is using the densely covered capillary tube of crystallizer surface, hair
The vegetable oil such as Oleum Glycines are filled with tubule or the preferable lubricating oil of some high-temperature behaviors is lubricated the demoulding, overcome lacking for the above
Point, but the capillary tube mould oil that uses at present is often due to performance is bad, causes carbon deposit serious, and capilar bore is frequently occluded,
Casting stripping result is affected, while smoldering serious.
For problem above, research staff is developed such as publication number：103084539A, patent name：Aluminium alloy casting knot
The patent of brilliant device capillary tube mould oil and preparation method thereof, its component consists of two butane phosphite esters 3-5%；Polybutylene list
Butyl ether 95-97%.
The mould oil summer or can meet requirement during higher workshop temperature in actual applications, particularly, but
To winter, will go wrong, such as：Because the kinematic viscosity of product is high, filling is not easy, and is covered with the time of whole capillary tube
It is long；Due also to the physical and chemical index of product is unique, it is difficult to be diluted with the material of other similar performances use.
While too high-viscosity mould oil is bad due to mobility, ooze out slow；The too low mould oil of viscosity is due to mobility
It is very good, ooze out fast so that too high with oil mass；Can cause surface lubrication bad.
The content of the invention
In view of disadvantages described above, the purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of polymethylacrylic acid phosphorus
Acid esters and preparation method thereof and prepare aluminum casting crystallizer mould oil with the ester.
For achieving the above object, the invention provides a kind of polymethylacrylic acid phosphate ester, by the thing including following components
Matter is prepared from：Methacrylic acid, fatty alcohol, polyhydric alcohol, phosphoric acid；
Wherein, above-mentioned methacrylic acid and the mol ratio of-OH of fatty alcohol+polyhydric alcohol are 1：1~1.5；
Above-mentioned fatty alcohol is 1 with the-OH mol ratios of polyhydric alcohol：1~1.5；
It is 2-3% that above-mentioned phosphoric acid effective ingredient accounts for the percentage by weight of total component；
One or more mixture of the above-mentioned fatty alcohol in the saturation or unsaturated fatty alcohol of C10-C20；
Preferably, above-mentioned fatty alcohol selected from Decanol, lauryl alcohol, isomery lauryl alcohol, isomerous tridecanol, isomery tetradecyl alchohol,
The mixture of one or more in isomery pentadecanol, isomery hexadecanol, oleyl alcohol, isomery eicosanol, stearyl alcohol.
Above-mentioned polyhydric alcohol is in glycerol, trimethylolpropane, Mannitol, anhydrous sorbitol, glucose, Fructose, sucrose
The mixture of one or more.
Additionally, present invention also offers the manufacture method of above-mentioned polymethylacrylic acid phosphate ester：By methacrylic acid, phosphoric acid
First carry out after esterification with fatty alcohol, polyhydric alcohol, adding initiator carries out what polyreaction was prepared from.
The concrete technology step of above-mentioned polymethylacrylic acid phosphate ester is as follows：
Step one：Methacrylic acid, phosphoric acid and fatty alcohol, polyhydric alcohol are added in reactor, nitrogen is filled with and is changed out instead
Air in kettle is answered, is reacted 3~5 hours under 180~220 DEG C of reaction temperature；Moisture, as methyl-prop are discharged in decompression after reaction
Olefin(e) acid phosphate ester；
Step 2, the addition initiator stirring toward in reactor, keep reaction temperature to be 160-180 DEG C, polyreaction 4~8
After hour, the polymer in reactor is discharged, the temperature more than 100 DEG C is filtered and goes the removal of impurity, as polymethylacrylic acid
Phosphate ester.
Above-mentioned initiator is selected from dibenzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide
Hydrogen, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester, peroxide
Change butanone, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, peroxy dicarbonate
One kind in ethylhexyl, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile)；The usage amount of above-mentioned initiator is preferably metering system
The 0.5~1% of sour weight.
Additionally, present invention also offers a kind of aluminum casting crystallizer mould oil, manufactures the original of aluminum casting crystallizer mould oil
Include the polymethylacrylic acid phosphate ester of said method preparation in material, and the consumption of the polymethylacrylic acid phosphate ester is raw material
The 1-99% of gross mass.
In addition, present invention also offers the preferred version of above-mentioned aluminum casting crystallizer mould oil, i.e., by following weight percent
It is fabricated by than the component of content：
Polymethylacrylic acid phosphate ester 25-75%；
Polyol ester 25-75%；
Detergent-dispersant additive 0.1-0.5%.
Wherein, above-mentioned polyol ester carries out the conjunction obtained by esterification synthetic selected from polyhydric alcohol and unary fatty acid
The mixture of one or more in ester or natural fat acid polyol ester；
Preferably, the polyol ester of above-mentioned synthesis class preferably is selected from trimethylolpropane tris oleate, the Oleic acid of tetramethylolmethane four
Ester, Bis(pentaerythritol) oleate, trimethylolpropane tris cetylate, the cetylate of tetramethylolmethane four, Bis(pentaerythritol) Petiolus Trachycarpi
The mixture of one or more in acid esters.
Above-mentioned detergent-dispersant additive is selected from succimide class compound, preferred marque：T151、T152、T154、
One or more mixture in T155, T161.
In addition, present invention also offers the preparation method of above-mentioned aluminum casting crystallizer mould oil, by above-mentioned each component not
When mixing to transparent at a temperature of more than 100 DEG C, pack after cooling.
The effect of invention and effect
The polymethylacrylic acid phosphate ester prepared using the present invention, with higher burning-point, while effectively preventing burning, is subtracted
The usage amount of few releasing agent, carbon residue is few after burning, there is preferable lubricity, there is higher kinematic viscosity.Additionally, according to the present invention
Selection and proportioning, the polymethylacrylic acid phosphate ester of its manufacture is due to the fatty alcohol of long-chain possessed in its specific structure
Structure, the product for making the present invention has lower vitrifying point compared with traditional product.
Polyol ester has excellent lubricity and higher burning-point, and carbon residue is few after burning, with polymethyl acid phosphoric acid
Ester has good intermiscibility, and the kinematic viscosity of aluminum casting crystallizer mould oil can be adjusted by actually used requirement, meets actual
Production requirement.
Detergent-dispersant additive can effectively reduce when in use the generation of carbon deposit after burning.
Thus, in the present invention, above-mentioned each component is combined with preferred proportioning, realizes the organic of each component and melt
Close, by forming an aluminum casting crystallizer demoulding oil body stable, that dispersed, dynamic viscosity is moderate the characteristics of each component
System.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and have in below (eg embodiment)
Can be combined with each other between each technical characteristic of body description, so as to constitute new or preferred technical scheme.As space is limited, exist
This no longer tires out one by one states.
Specific embodiment
With reference to being embodied as, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition,
Or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage ratio and number are calculated by weight.The present invention is implemented
Raw materials used or instrument in example, if not special instruction, commercially available.
Embodiment one
Step one：By 8609g (100mol) methacrylic acids and 1180g phosphoric acid (valid density 50%) and 9319g Laurels
Alcohol (50mol) and 1841.8g (20mol) glycerol are added in reactor, are filled with nitrogen and are changed out air in reactor, in 180 DEG C
Reaction temperature under react 5 hours；Moisture, as methacrylic acid phosphoric acid ester are discharged in decompression after reaction；
Step 2, the addition 86g initiators dibenzoyl peroxide stirring toward in reactor, keep reaction temperature to be 180 DEG C,
After polyreaction 4 hours, the polymer in reactor is discharged, the temperature more than 100 DEG C is filtered and goes the removal of impurity, as poly- first
Based polyacrylic acid phosphate ester.
By above-mentioned poly- methyl polyacrylic acid phosphate ester 7500g, the peace and quiet dispersions of trimethylolpropane tris oleate 2450g, 50g
Agent T151 is stirred 20 minutes at a temperature of 100 DEG C or so, as a kind of aluminum casting crystallizer mould oil, natural cooling packaging.
Embodiment two
Step one：By 8609g (100mol) methacrylic acids and 597g phosphoric acid (valid density 85%) and 10019g isomeries
Tridecanol (50mol) and 2683.4g (20mol) trimethylolpropane are added in reactor, are filled with nitrogen and are changed out in reactor
Air, reacts 3 hours under 220 DEG C of reaction temperature；Moisture, as methacrylic acid phosphoric acid ester are discharged in decompression after reaction；
Step 2, the addition 45g lauroyl peroxides stirring toward in reactor, keep reaction temperature to be 160 DEG C, polyreaction
After 8 hours, the polymer in reactor is discharged, the temperature more than 100 DEG C is filtered and goes the removal of impurity, as polymethylacrylic acid
Phosphate ester.
By above-mentioned polymethylacrylic acid phosphate ester 2500g, oleate 6990kg, 10g detergent-dispersant additive of tetramethylolmethane four
T152, at a temperature of 100 DEG C or so stir 20 minutes, as a kind of aluminum casting crystallizer mould oil, natural cooling packaging.
Embodiment three
Step one：By 8609g (100mol) methacrylic acids and 1178g phosphoric acid (valid density 50%) and 14550g isomeries
Hexadecanol (60mol) and 1821.7g (10mol) Mannitol are added in reactor, are filled with nitrogen and are changed out air in reactor, in
React 4 hours under 200 DEG C of reaction temperature；Moisture, as methacrylic acid phosphoric acid ester are discharged in decompression after reaction；
Step 2, the addition 60g tert-butyl hydroperoxide stirring toward in reactor, keep reaction temperature to be 170 DEG C, and polymerization is instead
After answering 6 hours, the polymer in reactor is discharged, the temperature more than 100 DEG C is filtered and goes the removal of impurity, as polymethyl
Acid phosphoric acid ester.
By above-mentioned polymethylacrylic acid phosphate ester 5000g, Bis(pentaerythritol) oleate 4970kg, 30g detergent-dispersant additive
T154 is stirred 20 minutes at a temperature of 100 DEG C or so, as a kind of aluminum casting crystallizer mould oil, natural cooling packaging.
The physical and chemical index of aluminum casting crystallizer mould oil obtained above is as follows：
Example IV
Step one：By 8609g (100mol) methacrylic acids and 917g phosphoric acid (concentration 50%) and 9497.4g Decanols
(60mol) add in reactor with 1641.6g (10mol) anhydrous sorbitol, be filled with nitrogen and change out air in reactor, in
React 4 hours under 210 DEG C of reaction temperature；Moisture, as methacrylic acid phosphoric acid ester are discharged in decompression after reaction；
Step 2, the addition 50g di-t-butyl peroxides stirring toward in reactor, keep reaction temperature to be 175 DEG C, and polymerization is instead
After answering 3.5 hours, the polymer in reactor is discharged, the temperature more than 100 DEG C is filtered and goes the removal of impurity, as poly- methyl-prop
Olefin(e) acid phosphate ester.
By above-mentioned polymethylacrylic acid phosphate ester 4000g, peace and quiet point of trimethylolpropane tris cetylate 5980kg, 20g
Powder T155 is stirred 20 minutes at a temperature of 100 DEG C or so, as a kind of aluminum casting crystallizer mould oil, natural cooling bag
Dress.
Embodiment five
Step one：By 8609g (100mol) methacrylic acids and 1400g phosphoric acid (concentration 50%) and 18794.3g oleyl alcohol
(70mol) add in reactor with 1801.6g (10mol) glycerol, be filled with protection gas shift and go out air in reactor, in 170 DEG C
Reaction temperature under react 4 hours；Moisture, as methacrylic acid phosphoric acid ester are discharged in decompression after reaction；
Step 2, the addition 70g azodiisobutyronitriles stirring toward in reactor, keep reaction temperature to be 170 DEG C, polyreaction
After 6 hours, the polymer in reactor is discharged, the temperature more than 100 DEG C is filtered and goes the removal of impurity, as polymethylacrylic acid
Phosphate ester.
By above-mentioned polymethylacrylic acid phosphate ester 3400g, the cetylate 3000g of tetramethylolmethane four, Bis(pentaerythritol) Petiolus Trachycarpi
Acid esters 3560g, 40g detergent-dispersant additive T161 is stirred 20 minutes at a temperature of 100 DEG C or so, as a kind of aluminum casting crystallizer
Mould oil, natural cooling packaging.
The physical and chemical index of aluminum casting crystallizer mould oil obtained above is as follows：
The all documents referred in the present invention are all incorporated as in this application reference, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned teachings for having read the present invention, those skilled in the art can
To make various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (10)
1. a kind of polymethylacrylic acid phosphate ester, it is characterised in that be prepared from by the material including following components：Metering system
Acid, fatty alcohol, polyhydric alcohol, phosphoric acid；
The methacrylic acid is 1 with the mol ratio of-OH of fatty alcohol+polyhydric alcohol：1~1.5；
The fatty alcohol is 1 with the-OH mol ratios of polyhydric alcohol：1~1.5；
It is 2-3% that the phosphoric acid effective ingredient accounts for the percentage by weight of total component.
2. polymethylacrylic acid phosphate ester as claimed in claim 1, it is characterised in that the fatty alcohol is selected from C10-C20's
The mixture of one or more in saturation or unsaturated fatty alcohol；Preferably, above-mentioned fatty alcohol selected from Decanol, lauryl alcohol,
Isomery lauryl alcohol, isomerous tridecanol, isomery tetradecyl alchohol, isomery pentadecanol, isomery hexadecanol, oleyl alcohol, isomery eicosanol, stearyl alcohol
In the mixture of one or more.
3. polymethylacrylic acid phosphate ester as claimed in claim 1, it is characterised in that the polyhydric alcohol is selected from glycerol, three hydroxyls
The mixture of one or more in methylpropane, Mannitol, anhydrous sorbitol, glucose, Fructose, sucrose.
4. the manufacture method of the polymethylacrylic acid phosphate ester as described in any one of claim 1-3, it is characterised in that by methyl
Acrylic acid, phosphoric acid and fatty alcohol, polyhydric alcohol are first carried out after esterification, are added initiator and are carried out polyreaction and are prepared from
's.
5. the manufacture method of polymethylacrylic acid phosphate ester as claimed in claim 4, it is characterised in that concrete technology step is such as
Under：
Step one：Methacrylic acid, phosphoric acid and fatty alcohol, polyhydric alcohol are added in reactor, nitrogen is filled with and is changed out reactor
Interior air, reacts 3~5 hours under 180~220 DEG C of reaction temperature；Moisture, as methacrylic acid are discharged in decompression after reaction
Phosphate ester；
Step 2：Initiator stirring is added toward in reactor, keeps reaction temperature to be 160-180 DEG C, polyreaction 4~8 hours
Afterwards, the polymer in reactor is discharged, the temperature more than 100 DEG C is filtered and goes the removal of impurity, as polymethyl acid phosphoric acid
Ester.
6. the manufacture method of polymethylacrylic acid phosphate ester as claimed in claim 5, it is characterised in that the initiator is selected from
Dibenzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, peroxide
Change diisopropylbenzene (DIPB), peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide,
Di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, peroxy dicarbonate ethylhexyl, the isobutyl of azo two
One kind in nitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile)；
The usage amount of above-mentioned initiator is preferably the 0.5~1% of methacrylic acid weight.
7. a kind of aluminum casting crystallizer mould oil, it is characterised in that include in the raw material of manufacture aluminum casting crystallizer mould oil
Polymethylacrylic acid phosphate ester prepared by manufacture method described in any one of claim 4-6, and the polymethylacrylic acid phosphate ester
Consumption for raw material gross mass 1-99%.
8. aluminum casting crystallizer mould oil as claimed in claim 7, it is characterised in that by the group of following weight percent content
Divide and be fabricated by：
Polymethylacrylic acid phosphate ester 25-75%；
Polyol ester 25-75%；
Detergent-dispersant additive 0.1-0.5%.
9. aluminum casting crystallizer mould oil as claimed in claim 8, it is characterised in that
The polyol ester carries out the synthetic ester or day obtained by esterification synthetic selected from polyhydric alcohol and unary fatty acid
The mixture of one or more in right polyol esters of fatty acids；
Preferably, the polyol ester of above-mentioned synthesis class preferably is selected from the trimethylolpropane tris oleate, oleate of tetramethylolmethane four, double
In PETO, trimethylolpropane tris cetylate, the cetylate of tetramethylolmethane four, Bis(pentaerythritol) cetylate
The mixture of one or more；
The detergent-dispersant additive preferably is selected from succimide class compound, preferred marque：T151、T152、T154、T155、
One or more mixture in T161.
10. the preparation method of the aluminum casting crystallizer mould oil as described in any one of claim 7-9, it is characterised in that will be upper
Each component is stated when mixing to transparent at a temperature of less than 100 DEG C, is packed after cooling.
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| CN201610815870.3A CN106674398B (en) | 2016-09-08 | 2016-09-08 | Polymethacrylic acid phosphate, preparation method thereof and aluminum casting crystallizer mold release oil prepared from polymethacrylic acid phosphate |
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| CN201610815870.3A CN106674398B (en) | 2016-09-08 | 2016-09-08 | Polymethacrylic acid phosphate, preparation method thereof and aluminum casting crystallizer mold release oil prepared from polymethacrylic acid phosphate |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072776A (en) * | 1974-10-19 | 1978-02-07 | Hoechst Aktiengesellschaft | Process for the flameproofing of textile materials |
| EP0120559B1 (en) * | 1983-01-27 | 1988-12-14 | Kuraray Co., Ltd. | Adhesive |
| CN1683376A (en) * | 2005-02-23 | 2005-10-19 | 华南师范大学 | Monoester phosphate containing meth-acrylate structure, its preparing method and use |
| CN101161333A (en) * | 2006-10-11 | 2008-04-16 | 西北师范大学 | Methacrylic acid phosphoric acid ester slushing polymerisable emulsifier and its preparing method |
| CN101864012A (en) * | 2009-03-30 | 2010-10-20 | 罗门哈斯公司 | Improved polymerisable compound |
| CN103168055A (en) * | 2010-10-19 | 2013-06-19 | 丰田自动车株式会社 | Phosphonic acid polymer, production method of same, and electrolyte film fuel cell |
| CN104829764A (en) * | 2015-03-13 | 2015-08-12 | 上海金兆节能科技有限公司 | Butenedioic acid resin, preparation method thereof, and preparation of aluminum-casted crystallizer demoulding oil therewith |
-
2016
- 2016-09-08 CN CN201610815870.3A patent/CN106674398B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072776A (en) * | 1974-10-19 | 1978-02-07 | Hoechst Aktiengesellschaft | Process for the flameproofing of textile materials |
| EP0120559B1 (en) * | 1983-01-27 | 1988-12-14 | Kuraray Co., Ltd. | Adhesive |
| CN1683376A (en) * | 2005-02-23 | 2005-10-19 | 华南师范大学 | Monoester phosphate containing meth-acrylate structure, its preparing method and use |
| CN101161333A (en) * | 2006-10-11 | 2008-04-16 | 西北师范大学 | Methacrylic acid phosphoric acid ester slushing polymerisable emulsifier and its preparing method |
| CN101864012A (en) * | 2009-03-30 | 2010-10-20 | 罗门哈斯公司 | Improved polymerisable compound |
| CN103168055A (en) * | 2010-10-19 | 2013-06-19 | 丰田自动车株式会社 | Phosphonic acid polymer, production method of same, and electrolyte film fuel cell |
| CN104829764A (en) * | 2015-03-13 | 2015-08-12 | 上海金兆节能科技有限公司 | Butenedioic acid resin, preparation method thereof, and preparation of aluminum-casted crystallizer demoulding oil therewith |
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