CN112300439A - Ester plasticizer and application thereof - Google Patents
Ester plasticizer and application thereof Download PDFInfo
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- CN112300439A CN112300439A CN202011311467.XA CN202011311467A CN112300439A CN 112300439 A CN112300439 A CN 112300439A CN 202011311467 A CN202011311467 A CN 202011311467A CN 112300439 A CN112300439 A CN 112300439A
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- alcohol
- chlorine
- containing resin
- resin composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention provides an ester plasticizer obtainable by reacting the following (a) and (b): (a) an alcohol mixture produced from the reaction of a mixture of alcohols having an average carbon number of from greater than 10 to less than 12, the average carbon number determined by the formula:
wherein XiIs the mole fraction of alcohol (i); cniRepresents the number of carbon atoms in the alcohol (i); j is the lowest number of carbons in the alcohol group of the ester and must be at least 8; z is the highest number of carbons in the alcohol and is at most 15; and at leastIs a mixture of 4 or more alkyl alcohols, preferably at least 5 or more alkyl alcohols; (b) a polycarboxylic acid or anhydride thereof; the compositions of the present invention can be used as plasticizers, and the applicants have surprisingly found that they have improved mechanical and cold resistance properties, in particular lower volatility properties, when used in chlorine-containing resin compositions, for example softening temperatures of between-42 ℃ and-48 ℃, 175 ℃ and 60min volatility of between 1.2 and 2.5%, and 175 ℃ and 60min volatility of between 3.2 and 4.8%.
Description
The present application is a divisional application of the following applications: application date: 1 month and 2 days 2018; application No.: 2018100019415, respectively; the invention name is as follows: "an ester plasticizer and its application".
Technical Field
The invention relates to an ester plasticizer and a chlorine-containing resin composition (particularly a PVC composition) containing the ester plasticizer.
Background
Plasticizers are additives that increase the flexibility, pliability, and plasticity or flowability of the material, and the use of plasticizers is generally used to shift the thermoplastic range of the plastic to lower temperatures to achieve the desired elastic properties at lower processing and use temperature ranges, with soft/semi-soft PVC products currently being the primary consumer direction for plasticizers. Currently, the mainstream plasticizers are classified into aliphatic dibasic acid esters, phthalic acid esters (including phthalic acid esters and terephthalic acid esters), benzene polycarboxylic acid esters, benzoic acid esters, polyol esters, citric acid esters, polyesters and the like from chemical structure, however, these products are harmful to human bodies due to endocrine system destruction by environmental hormones, or have limitations in improving physical properties of the products in terms of processability, cold resistance, volatilization reduction, migration loss, thermal stability and the like. The current leading research on small-molecule ester plasticizers includes:
CN107250098A discloses an ester plasticizer, obtainable by reacting the following (a) and (b): (a) an alcohol mixture comprising (i) 20 to 50 wt% of ethylhexanol, based on the total weight of the alcohol mixture, (ii) 40 to 64 wt% of propylheptanol, based on the total weight of the alcohol mixture, (iii) 0 to 20 wt% of other alcohols, based on the total weight of the alcohol mixture; (b) polycarboxylic acids or anhydrides thereof.
CN106164164A discloses a plasticizer for vinyl chloride resins, which contains a non-phthalic acid ester (C) obtained by reacting a polycarboxylic acid (a) with an alcohol (B), wherein: (i) the polycarboxylic acid (a) is a polycarboxylic acid compound selected from the group consisting of alicyclic dicarboxylic acids, aromatic tricarboxylic acids, and derivatives thereof; (ii) the alcohol (B) is a saturated aliphatic alcohol (B1) containing a C9 saturated aliphatic alcohol as a main component; (iii) the saturated aliphatic alcohol (B1) contains 60 wt% or more of a straight-chain C9 saturated aliphatic alcohol (B1-1) and 40 wt% or less of a branched-chain C9 saturated aliphatic alcohol (B1-2); (iv) the linear chain ratio of the alcohol (B1) is 60% or more; and (v) the non-phthalic acid ester (C) contains substantially no phthalic acid ester obtained by reacting a phthalic acid compound or a derivative thereof with an alkyl alcohol having 8 or less carbon atoms.
CN 107011535A discloses a mixture of triisopentyl esters of trimellitic acid containing isomeric pentyl groups, wherein more than 5 mole% of the attached isomeric pentyl groups in the ester mixture are branched; they have good compatibility with PVC and PVC-containing polymers and at the same time exhibit a low migration tendency.
CN 107250099a discloses an ester plasticizer composition, which contains the following compounds:
however, the above studies have not been satisfactory for the improvement of the volatilization loss, the migration loss and the thermal stability as well as the various physical properties such as processability with resin, absorption rate, cold resistance, tensile strength and elongation.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ester composition, a plasticizer composition containing the ester composition, and a chlorine-containing resin composition. The technical difficulty of the invention lies in the selection of alkyl alcohol when synthesizing ester compounds, as mentioned in the background art, the carbon number of alkyl alcohol of ester plasticizer in the prior art is generally less than 9, and the single alkyl alcohol synthetic ester is used as the main stream, and the average carbon number is less than 9 when a few alkyl alcohol is compounded, the reason is that the ester plasticizer synthesized by alkyl alcohol with more than 9 carbon atoms has poor mechanical property although the volatility is reduced; in addition, although the field of plasticizers has a semi-empirical theory, the predictability is not strong, which is also a bottleneck limiting the development of plasticizers. The inventor unexpectedly discovers that when the alkyl alcohol with the average carbon number of 9-12 is used to synthesize the ester plasticizer, the mechanical property, the cold resistance, the low volatility and the like of the obtained chlorine-containing resin composition (particularly PVC composition) are obviously improved,
the technical scheme of the invention is as follows:
1. an ester composition obtainable by reacting the following (a) and (b):
(a) an alcohol mixture produced from the reaction of a mixture of alcohols having an average carbon number of from greater than 10 to less than 12, the average carbon number determined by the formula:
wherein XiIs the mole fraction of alcohol (i); cniRepresents the number of carbon atoms in the alcohol (i); j is the lowest number of carbons in the alcohol group of the ester and must be at least 8; z is the highest number of carbons in the alcohol and is at most 15; and at least 4 or more alkyl alcohols, preferably at least 5 or more alkyl alcohols;
(b) a polycarboxylic acid or anhydride thereof selected from the group consisting of mellitic acid, trimellitic acid, pyromellitic acid, hemimellitic acid, trimesic acid, naphthalene tricarboxylic acid, anthracene tricarboxylic acid, biphenyl tricarboxylic acid, mixtures thereof and positional isomers of the foregoing acids.
Preferably, the polycarboxylic acid is trimellitic acid.
Preferably, the polycarboxylic acid is pyromellitic acid.
Preferably, j is at least 9.
Preferably, z is at most 14.
Preferably, the content of branched alcohol in the alcohol is 15 to 70%.
Preferably, the content of branched alcohols in the alcohol is 15-60%, preferably 15-35%.
The invention also provides a plasticizer composition which contains any one of the ester compositions.
The present invention also provides a chlorine-containing resin composition comprising the plasticizer composition according to claim.
Preferably, the chlorine-containing resin comprises homopolymerized PVC, copolymerization modified PVC, homopolymerized CPVC and copolymerization modified CPVC.
Advantageous effects
The present invention provides an ester composition which can be used as a plasticizer, and the applicant has surprisingly found that when used in a chlorine-containing resin composition, the ester composition has improved mechanical properties and cold resistance, and particularly has lower volatility, for example, the softening temperature can be between-42 ℃ and-48 ℃, the volatilization volume at 175 ℃ and 60min is between 1.2 and 2.5 percent, and the volatilization volume at 175 ℃ and 60min is between 3.2 and 4.8 percent.
Detailed Description
The ester compounds of the present invention are the core of the realisation of the present invention, and as is well known, the esterification of acids with alcohols is the fundamental reaction in the field of chemical synthesis and generally comprises a) heating a mixture consisting essentially of an acid component or its anhydride and an alcohol component to boiling in a reaction zone in the presence of an esterification catalyst, b) separating a vapour comprising alcohol and water into an alcohol-rich fraction and a water-rich fraction by rectification, and c) returning the alcohol-rich fraction to the reaction zone and removing the water-rich fraction from the process, the synthesis of the ester composition of the present invention also following the above-described procedure.
The esterification catalyst comprises an acidic catalyst and an amphoteric catalyst. The acidic catalyst, for example, an inorganic acid such as sulfuric acid and phosphoric acid; organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid; the amphoteric catalyst includes a titanium compound, a tin (IV) compound or a zirconium compound, such as a titanium tetraalkoxide, e.g., titanium tetrabutoxide, and tin (IV) oxide. The esterification catalyst is used in an amount of usually 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on the sum of the acid component (or anhydride) and the alcohol component. The invention is further illustrated by the following specific examples.
Preparation examples 1 to 8: synthesis of ester compositions
The alcohol mixture and the acid compound are weighed according to the feeding ratio shown in the table 1, 0.5wt% of stannous oxalate catalyst is added, the mixture is heated to reflux slowly, reduced pressure distillation is started for 6 hours after 0.5 hour, when the acid value is reduced to be below 0.8, the heating temperature is reduced, the vacuum degree is further reduced, so that the unreacted alcohol is removed, and then the mixture is neutralized, filtered, washed and desolventized. Incidentally, the preparation example is designated as Ax, and the preparation comparative example is designated as Acx, wherein x is the experiment number; the application examples are described as Sx, and the comparative examples are denoted as Scx, wherein x is the application example number.
TABLE 1 charges of preparation examples 1 to 8
Application examples
100 parts of PVC, 3 parts of calcium-zinc stabilizer, 5 parts of epoxidized soybean oil, 2 parts of ACR and 2 parts of light stabilizer are taken, 40 parts of ester plasticizer composition obtained in the preparation example are mixed, mixed and extruded and molded at 170 ℃ by a double-screw extruder to obtain a 3mm pressing plate, and parameters of 100% tensile modulus, strength, elongation at break, softening temperature, volatilization amount and the like of the product are measured (the average value is obtained after each sample is measured for three times). Methods for measuring tensile modulus, strength, and elongation at break among the above properties are well known in the art and thus are not described in detail; for the softening temperature test, 5 prepared samples were left alone at a specific temperature for 3 minutes, then impacted, and the temperature at which 3 of the 5 samples were damaged was measured; as for the volatilization amount, after the prepared sample was left on the set temperature for a prescribed time, the weight of the sample was measured, where the volatilization loss (%) — (initial sample weight-sample weight after work)/initial sample weight) x 100%.
Table 2 application examples performance testing
| S1 | S2 | S3 | S4 | S5 | S6 | S7 | S8 | Sc1 | |
| Type of plasticizer | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | Ac1 |
| 100% tensile modulus/MPa | 17.8 | 12.9 | 13.5 | 15.2 | 16.8 | 13.2 | 14.1 | 15.7 | 9.5 |
| strength/Mpa | 36.5 | 30.2 | 33.4 | 35.5 | 36 | 29.8 | 32.5 | 34.8 | 21.3 |
| Elongation at break/% | 450 | 415 | 425 | 440 | 445 | 410 | 430 | 435 | 380 |
| Softening temperature/. degree.C | -48 | -42 | -44 | -46 | -47 | -43 | -45 | -46 | -38 |
| Volatile amount at 175 deg.C, 60 min% | 1.2 | 2.5 | 2.2 | 1.8 | 1.3 | 2.4 | 2.1 | 1.9 | 4.2 |
| Volatilization at 175 deg.C for 120 min% | 3.2 | 4.8 | 4.2 | 3.8 | 3.3 | 4.6 | 4.1 | 3.7 | 7.9 |
As can be seen from table 2, the application examples have excellent improvement effects in terms of mechanical properties (100% tensile modulus, strength, elongation at break), cold resistance (softening temperature), volatilization amount, and the like, and compared with the ester plasticizer composition with an average carbon number of about 9 (8.98 in Ac 1), the mechanical properties, cold resistance, and volatilization amount are significantly improved, for example, the softening temperature can be between-42 ℃ and-48 ℃, the volatilization amount at 175 ℃ and 60min is between 1.2% and 2.5%, and the volatilization amount at 175 ℃ and 60min is between 3.2% and 4.8%.
Claims (10)
1. A chlorine-containing resin composition comprising a plasticizer composition, characterized in that the plasticizer composition comprises an ester composition obtainable by reacting:
(a) an alcohol mixture made from the reaction of a mixture of alcohols having an average carbon number of from greater than 10 to less than 10.44, the average carbon number determined by the formula:
wherein XiIs the mole fraction of alcohol (i); cniRepresents the number of carbon atoms in the alcohol (i); j is the lowest number of carbons in the alcohol group of the ester and must be at least 8; z is the highest number of carbons in the alcohol and is at most 15; and at least 4 alkyl alcohols;
(b) a polycarboxylic acid or anhydride thereof selected from the group consisting of trimellitic acid, pyromellitic acid, mixtures thereof, and positional isomers of the foregoing
The catalyst for the reaction of (a) and (b) is an amphoteric catalyst, preferably stannous oxalate.
2. The chlorine-containing resin composition according to claim 1, wherein said alcohol mixture is a mixture of at least 5 alkyl alcohols.
3. The chlorine-containing resin composition as claimed in claim 1, wherein said polycarboxylic acid is trimellitic acid.
4. The chlorine-containing resin composition as claimed in claim 1, wherein said polycarboxylic acid is pyromellitic acid, preferably a mixture of trimellitic acid and pyromellitic acid.
5. The chlorine-containing resin composition as claimed in claim 1, wherein j is at least 9.
6. The chlorine-containing resin composition as claimed in claim 1, wherein z is at most 14.
7. The chlorine-containing resin composition according to claim 1, wherein the branched alcohol content of the alcohol is 15 to 70%.
8. The chlorine-containing resin composition according to claim 1, wherein the branched alcohol content of the alcohol is 15 to 60%.
9. The chlorine-containing resin composition according to claim 1, wherein the branched alcohol content of the alcohol is 15 to 35%.
10. The chlorine-containing resin composition of claim 1, wherein the chlorine-containing resin comprises homopolyPVC, copoly-modified PVC, homopoly-CPVC and copoly-modified CPVC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011311467.XA CN112300439B (en) | 2018-01-02 | 2018-01-02 | Ester plasticizer and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011311467.XA CN112300439B (en) | 2018-01-02 | 2018-01-02 | Ester plasticizer and application thereof |
| CN201810001941.5A CN108192133B (en) | 2018-01-02 | 2018-01-02 | Ester plasticizer and application thereof |
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| CN201810001941.5A Division CN108192133B (en) | 2018-01-02 | 2018-01-02 | Ester plasticizer and application thereof |
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| CN112300439B CN112300439B (en) | 2022-04-29 |
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| CN109053444B (en) * | 2018-09-05 | 2021-04-20 | 安徽泰达新材料股份有限公司 | High and low temperature resistant pyromellitic trimethyl acid synthetic ester plasticizer and preparation method thereof |
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| CN102002200A (en) * | 2001-09-25 | 2011-04-06 | 埃克森美孚化学专利公司 | Plasticised polyvinyl chloride |
| CN102224128A (en) * | 2008-11-24 | 2011-10-19 | 埃克森美孚化学专利公司 | Improved method for the manufacture of long chain phthalate dialkyl ester compositions |
| CN106164164A (en) * | 2014-03-27 | 2016-11-23 | 新日本理化株式会社 | Vinyl chloride resin plasticizer containing non-phthalic acid system ester and the vinyl chloride resin composition containing this plasticizer |
| CN107001748A (en) * | 2014-12-18 | 2017-08-01 | 花王株式会社 | Halogen system plasticizer for resin |
| CN107011535A (en) * | 2015-09-28 | 2017-08-04 | 赢创德固赛有限公司 | Three amyl group esters of trimellitic acid |
| US20170253723A1 (en) * | 2016-03-07 | 2017-09-07 | Exxonmobil Chemical Patents Inc. | Plasticizers Production and Use |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1988003155A1 (en) * | 1986-10-24 | 1988-05-05 | Allied Corporation | Polyester composition containing an ester of an ethoxylated aromatic alcohol |
| KR20110008631A (en) * | 2009-07-20 | 2011-01-27 | 에스케이이노베이션 주식회사 | Ester based plasticizer |
| KR20140027014A (en) * | 2012-08-23 | 2014-03-06 | 주식회사 엘지화학 | Plasticizer composition |
| CN102924280B (en) * | 2012-10-25 | 2015-08-19 | 浙江皇马科技股份有限公司 | A kind of preparation method of trimellitate |
| CN103012150A (en) * | 2012-12-27 | 2013-04-03 | 江南大学 | Method for preparing plasticizer 1, 2, 4-benzenetricarboxylicacid tris(2-propyl heptyl) ester |
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2018
- 2018-01-02 CN CN202011311467.XA patent/CN112300439B/en active Active
- 2018-01-02 CN CN201810001941.5A patent/CN108192133B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002200A (en) * | 2001-09-25 | 2011-04-06 | 埃克森美孚化学专利公司 | Plasticised polyvinyl chloride |
| CN102224128A (en) * | 2008-11-24 | 2011-10-19 | 埃克森美孚化学专利公司 | Improved method for the manufacture of long chain phthalate dialkyl ester compositions |
| CN106164164A (en) * | 2014-03-27 | 2016-11-23 | 新日本理化株式会社 | Vinyl chloride resin plasticizer containing non-phthalic acid system ester and the vinyl chloride resin composition containing this plasticizer |
| CN107001748A (en) * | 2014-12-18 | 2017-08-01 | 花王株式会社 | Halogen system plasticizer for resin |
| CN107011535A (en) * | 2015-09-28 | 2017-08-04 | 赢创德固赛有限公司 | Three amyl group esters of trimellitic acid |
| US20170253723A1 (en) * | 2016-03-07 | 2017-09-07 | Exxonmobil Chemical Patents Inc. | Plasticizers Production and Use |
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| Publication number | Publication date |
|---|---|
| CN112300439B (en) | 2022-04-29 |
| CN108192133B (en) | 2021-01-12 |
| CN108192133A (en) | 2018-06-22 |
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