CN103319698B - A kind of Polymer polyester plasticizer and its preparation method and application - Google Patents
A kind of Polymer polyester plasticizer and its preparation method and application Download PDFInfo
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- CN103319698B CN103319698B CN201310244270.2A CN201310244270A CN103319698B CN 103319698 B CN103319698 B CN 103319698B CN 201310244270 A CN201310244270 A CN 201310244270A CN 103319698 B CN103319698 B CN 103319698B
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Abstract
The present invention relates to a kind of Polymer polyester plasticizer, it is that raw material is prepared from 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid, and the molecular-weight average of described Polymer polyester plasticizer is 2500 ~ 5500, acid value≤1, the viscosity of 25 DEG C is 1.5 ~ 3.5Pas.Good viscosity is had relative to other polymeric plasticizer, mobility is relatively better, be conducive to processing, especially in the lower situation of temperature in winter, too full-bodied polymeric plasticizer needs to heat in advance and could normally use, low viscosity of the present invention can use at normal temperatures, reduce energy usage quantity and process period, and aging of the present invention, oil-proofness are excellent, thus tool has been widely used, can as the softening agent of polyvinyl chloride or rubber ink.
Description
Technical field
The present invention relates to a kind of Polymer polyester plasticizer and preparation method thereof and its application in polyvinyl chloride or rubber ink plasticising.
Background technology
Phthalate compound is most widely used softening agent in the world, and they are used in the production process of plastics, coating, printing and dyeing, makeup and spices, but this series products is subject to the query of people about its security always for a long time.In the last few years, the output of this compounds constantly increased, and it is entered environment constantly, had become the most general global first kinds of pollution matter.On October 28th, 2008, EU chemicals management board ECHA was by three kinds of phthalates, that is: dibutyl phthalate (DBP), phthalic acid (2-ethyl hexyl) ester (DEHP) and butyl benzyl phthalate (BBP) are included the SVHC(licensed in and shown great attention to thing) candidate substances inventory.And SVHC candidate substances inventory meeting regular update, kind only can increase and can not reduce.According to the requirement of EU chemicals management law REACH regulation, forbid using SVHC in all products of providing or material, total amount requires to be less than 1000ppm(by weight), otherwise supplier is obligated notifies human consumer, if and human consumer wonders SVHC information, European Union's importor must provide relevant information in 45 days; And the show great attention to thing SVHC of article in year sales volume is greater than 1 ton hour and must circulates a notice of EU chemicals management board ECHA authorization and just can enter EU market and sell.At present, various countries not only only have DBP for the restriction of phthalate compound, DEHP, BBP tri-kinds, almost cover all phthalates, include but not limited to: diisononyl phthalate (DINP), Di Iso Decyl Phthalate (DIDP), dinoctyl phthalate (DNOP), diisobutyl phthalate (DIBP), Dinonylphthalate (DNP), dicyclohexyl phthalate (DCHP), diheptyl phthalate (DHP), dimixo-octyl phthalate (DIOP), dimethyl phthalate (DMP), diethyl phthalate (DEP), dipropyl phthalate (DPRP), diphenyl phthalate (DPP) etc.Dimethyl phthalate (DMP), dibutyl phthalate (DBP) and dioctyl phthalate (DOP) (DOP) are listed in the Black List of China's priority pollutant by China.
Therefore, be necessary the substitute that a kind of phthalate compound softening agent is provided, to overcome the defect that it exists in the prior art.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of with PVC compatible good, Polymer polyester plasticizer that plasticization efficiency is high.
Another object of the present invention is to the preparation method that a kind of Polymer polyester plasticizer is provided.
Another object of the present invention is to the application that a kind of Polymer polyester plasticizer is provided.
For solving the problem, the technical solution adopted in the present invention is as follows:
A kind of Polymer polyester plasticizer, it is characterized in that: be that raw material is prepared from 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid, the molecular-weight average of described Polymer polyester plasticizer is 2500 ~ 5500, acid value≤1, the viscosity of 25 DEG C is 1.5 ~ 3.5Pas.
Preferably, the molecular-weight average of described Polymer polyester plasticizer is the viscosity measured by 3800 ~ 4800,25 DEG C is 2.0 ~ 3.0Pas.
As further technical scheme of the present invention, described raw material 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid feed intake by weight for 0.34:0.2:0.418:1.
A preparation method for Polymer polyester plasticizer, is characterized in that comprising the following steps:
(1) by 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid are by weight adding in reactor for 0.34:0.2:0.418:1, feeding sequence is: 2-propyl enanthol, 1,3-dimethyl propylene glycol, catalyst for esterification reaction, neopentyl glycol, finally add hexanodioic acid, stir;
(2) normal pressure intensification esterification: reactive tank temperature is set as 150 DEG C ~ 170 DEG C, in reaction process, discharge water and the alcohol of reaction generation, alcohol reflux is to reactor;
(3) normal pressure holds warm esterification: raising temperature of reaction is 220 DEG C ~ 230 DEG C, question response acid value 10 ~ 15, viscosity 0.9 ~ 1.2Pas, and normal pressure is held warm esterification and terminated;
(4) negative pressure transesterification reaction: vacuumize, control reactive tank temperature and be set as 220 DEG C ~ 230 DEG C, to reaction end acid value≤1, viscosity 2.0 ~ 3.0Pas, namely completes negative pressure transesterification reaction;
(5) be cooled to 0 DEG C ~ 40 DEG C, namely obtain Polymer polyester plasticizer.
As further technical scheme of the present invention, described catalyst for esterification reaction is one or both in tin oxalate and triphenyl phosphite.Catalyzer of the present invention can be used alone tin oxalate or triphenyl phosphite, also can tin oxalate used in combination and triphenyl phosphite, and effect used in combination is best, also contributes to the generation reducing organotin.Tin oxalate also claims the sub-tin of oxalic acid or stannous oxalate, for the Primary Catalysts of esterification.Triphenyl phosphite also claims triphenyl, when taking tin oxalate as Primary Catalysts (stablizer), coordinating triphenyl phosphite can reduce the harm of metal chloride, keeping the transparency of Polymer polyester plasticizer, and suppress colour-change; Triphenyl phosphite is also a kind of well chemical intermediate, with halogenated flame retardant and use, can play the antioxidant effect of fire retardant, and have light stability concurrently, can be used as synthesis alkyd resin and polyester.
As further technical scheme of the present invention, step (2) normal pressure intensification reaction time of esterification is 1 ~ 2h.
As further technical scheme of the present invention, it is 4 ~ 5h that step (3) normal pressure holds warm reaction time of esterification.
As further technical scheme of the present invention, step (4) the negative pressure transesterification reaction time is 5 ~ 6h.
Described Polymer polyester plasticizer is preparing the application in pvc material or rubber ink.Polymer polyester plasticizer of the present invention, as the softening agent of PVC, can be used alone, and also can use together with the Conventional plasticizers of this area.Can by the every hectogram number of following amounts of components processing PVC: PVC100phr(), softening agent 40 ~ 60phr, stablizer 2 ~ 4phr.Wherein, described softening agent is Polymer polyester plasticizer of the present invention, or the mixture of one or more softening agent in Polymer polyester plasticizer of the present invention and phthalate, described stablizer is lead salt or lead-free calcium zinc, organotin, rare earth etc.
Compared to existing technology, beneficial effect of the present invention is:
1) Polymer polyester plasticizer of the present invention is non-phthalate compound, the present invention has good viscosity relative to other polymeric plasticizer, mobility is relatively better, be conducive to processing, especially in the lower situation of temperature in winter, too full-bodied polymeric plasticizer needs to heat in advance and could normally use, low viscosity of the present invention can use at normal temperatures, reduce energy usage quantity and process period, and aging of the present invention, oil-proofness are excellent;
2) compatibility of the present invention and PVC is good, and plasticization efficiency is high, improves class and the level of the plasthetics such as PVC, can be called permanent plasticizer, has higher marketable value;
3) resistance to transitional splendid to ABS and PS sheet material of PVC product of the present invention;
4) Polymer polyester plasticizer tool of the present invention has been widely used, can be used for the electric wire of PVC product, electric adhesive tape, gas pipe, rubber adhesive plaster, leather, auto parts machinery, can be used for the wire rod of 105 DEG C of (UL) lines and low temperature resistant wire rod, in electron device (as mobile phone air-conditioning refrigerator etc.), the coating of high temperature insulation part, also can be used for the softening agent of environment-friendly ink, food product packing film, beverage flexible pipe, bottle cap rubber cushion etc.
Embodiment
By 1020kg2-propyl enanthol, 600kg1,3-dimethyl propylene glycol, 1253kg neopentyl glycol and 3000kg hexanodioic acid add in reactor, and drop into catalyst for esterification reaction tin oxalate 0.51kg and triphenyl phosphite 0.6kg, stir, reactive tank temperature is set as 150 DEG C ~ 170 DEG C, in reaction process, discharges water and the alcohol of reaction generation, alcohol reflux, to reactor, reacts 1 ~ 2h; Raising temperature of reaction is 220 DEG C ~ 230 DEG C, reaction 4 ~ 5h, question response acid value 10 ~ 15, viscosity 0.9 ~ 1.2Pas, and normal pressure is held temperature reaction and terminated; Vacuumize, control reactive tank temperature and be set as 220 DEG C ~ 230 DEG C, reaction 5 ~ 6h, to reaction end acid value≤1, viscosity 2.0 ~ 3.0Pas, namely completes negative pressure transesterification reaction; Cooling obtains finished product and is Polymer polyester plasticizer.
By following amounts of components: the every hectogram number of PVCS-65 powder 100phr(), Polymer polyester plasticizer 50phr, stablizer 4phr, be processed into PVC plastic glue, and pulling-on piece condition is take out sheet 10min at 165 DEG C.Carried out physical property measurement and oil-proofness (diesel oil) testing experiment, oil-proofness (diesel oil) testing experiment condition is: under normal temperature, soaks 7 days in diesel oil.
The physical property of table 1 three kinds of softening agent compares
Note: PN-1030 is that Changchun, Taiwan company produces, and W-2050 is that Japanese DIC company produces.
Table 2 oil-proofness (diesel oil) is tested
Note: PN-1030 is that Changchun, Taiwan company produces, and W-2050 is that Japanese DIC company produces.
The present invention has good viscosity relative to other polymeric plasticizer as can be seen from Table 1, mobility is relatively better conducive to processibility, especially in the lower situation of temperature in winter, too full-bodied polymeric plasticizer needs to heat in advance and could normally use, and low viscosity of the present invention can use under normal temperature again and reduce the energy and use and process period.And aging of the present invention is excellent.Oil-proofness of the present invention is excellent as can be seen from Table 2.
Above-mentioned embodiment is only the preferred embodiment of the present invention; can not limit the scope of protection of the invention with this, change and the replacement of any unsubstantiality that those skilled in the art does on basis of the present invention all belong to the present invention's scope required for protection.
Claims (8)
1. a Polymer polyester plasticizer, it is characterized in that: be that raw material is prepared from 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid, the molecular-weight average of described Polymer polyester plasticizer is 2500 ~ 5500, acid value≤1, the viscosity of 25 DEG C is 1.5 ~ 3.5Pas;
Described raw material 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid feed intake by weight for 0.34:0.2:0.418:1;
Described Polymer polyester plasticizer, obtains as follows:
(1) by 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid are by weight adding in reactor for 0.34:0.2:0.418:1, feeding sequence is: 2-propyl enanthol, 1,3-dimethyl propylene glycol, catalyst for esterification reaction, neopentyl glycol, finally add hexanodioic acid, stir;
(2) normal pressure intensification esterification: reactive tank temperature is set as 150 DEG C ~ 170 DEG C, in reaction process, discharge water and the alcohol of reaction generation, alcohol reflux is to reactor;
(3) normal pressure holds warm esterification: raising temperature of reaction is 220 DEG C ~ 230 DEG C, question response acid value 10 ~ 15, viscosity 0.9 ~ 1.2Pas, and normal pressure is held warm esterification and terminated;
(4) negative pressure transesterification reaction: vacuumize, control reactive tank temperature and be set as 220 DEG C ~ 230 DEG C, to reaction end acid value≤1, viscosity 2.0 ~ 3.0Pas, namely completes negative pressure transesterification reaction;
(5) be cooled to 0 DEG C ~ 40 DEG C, namely obtain Polymer polyester plasticizer.
2. Polymer polyester plasticizer as claimed in claim 1, is characterized in that: the molecular-weight average of described Polymer polyester plasticizer is the viscosity of 3800 ~ 4800,25 DEG C is 2.0 ~ 3.0Pas.
3. a preparation method for Polymer polyester plasticizer as claimed in claim 1, is characterized in that comprising the following steps:
(1) by 2-propyl enanthol, 1,3-dimethyl propylene glycol, neopentyl glycol and hexanodioic acid are by weight adding in reactor for 0.34:0.2:0.418:1, feeding sequence is: 2-propyl enanthol, 1,3-dimethyl propylene glycol, catalyst for esterification reaction, neopentyl glycol, finally add hexanodioic acid, stir;
(2) normal pressure intensification esterification: reactive tank temperature is set as 150 DEG C ~ 170 DEG C, in reaction process, discharge water and the alcohol of reaction generation, alcohol reflux is to reactor;
(3) normal pressure holds warm esterification: raising temperature of reaction is 220 DEG C ~ 230 DEG C, question response acid value 10 ~ 15, viscosity 0.9 ~ 1.2Pas, and normal pressure is held warm esterification and terminated;
(4) negative pressure transesterification reaction: vacuumize, control reactive tank temperature and be set as 220 DEG C ~ 230 DEG C, to reaction end acid value≤1, viscosity 2.0 ~ 3.0Pas, namely completes negative pressure transesterification reaction;
(5) be cooled to 0 DEG C ~ 40 DEG C, namely obtain Polymer polyester plasticizer.
4. the preparation method of Polymer polyester plasticizer as claimed in claim 3, is characterized in that: described catalyst for esterification reaction is one or both in tin oxalate and triphenyl phosphite.
5. the preparation method of Polymer polyester plasticizer as claimed in claim 3, is characterized in that: step (2) normal pressure intensification reaction time of esterification is 1 ~ 2h.
6. the preparation method of Polymer polyester plasticizer as claimed in claim 3, is characterized in that: it is 4 ~ 5h that step (3) normal pressure holds warm reaction time of esterification.
7. the preparation method of Polymer polyester plasticizer as claimed in claim 3, is characterized in that: step (4) the negative pressure transesterification reaction time is 5 ~ 6h.
8. Polymer polyester plasticizer as claimed in claim 1 is preparing the application in pvc material or rubber ink.
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| CN104945607B (en) * | 2015-07-24 | 2016-08-24 | 山东万图高分子材料有限公司 | A kind of environmental protection polyester plasticizer and its preparation method and application |
| CN104945783B (en) * | 2015-07-24 | 2016-08-24 | 山东万图高分子材料有限公司 | A kind of PVC polyester plasticizer and its preparation method and application |
| CN105218797A (en) * | 2015-10-29 | 2016-01-06 | 林志鹏 | A kind of polymeric plasticizer and its preparation method and application |
| CN109651730B (en) * | 2018-12-07 | 2021-09-24 | 北京化工大学 | Multi-component copolyester plasticizer, preparation and application thereof |
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| ATE205509T1 (en) * | 1999-12-23 | 2001-09-15 | Basf Ag | POLYESTERS TERMINATED WITH ISOMERS NONANOLS, METHOD FOR THEIR PRODUCTION AND THEIR USE AS PLASTICIZERS |
| JP4204305B2 (en) * | 2002-11-08 | 2009-01-07 | 株式会社Ａｄｅｋａ | Polyester plasticizer and chlorine-containing resin composition |
| CN100584873C (en) * | 2006-07-03 | 2010-01-27 | 长春人造树脂厂股份有限公司 | Copolyester plasticizer for polyvinyl chloride plastic and polyvinyl chloride composition containing the same |
| CN101456945A (en) * | 2008-12-24 | 2009-06-17 | 郭立耀 | Method for producing low molecular weight polyester plasticiser |
| CN101602666B (en) * | 2009-07-07 | 2012-10-10 | 佛山市顺德区天晟贸易有限公司 | Adipic acid di-(2-propyl heptyl) phthalate and preparation method and application thereof |
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Effective date of registration: 20211021 Address after: 519000 port building 308-33 (centralized office area), No. 2001, gaolangang Avenue, Nanshui Town, gaolangang Economic Zone, Zhuhai City, Guangdong Province Patentee after: Zhuhai Shiyue New Material Co.,Ltd. Address before: No.309, building C, Shunde Creative Industrial Park, No.41 Fengxiang Road, Daliang Xinjiao, Shunde District, Foshan City, Guangdong Province 528300 Foshan City Patentee before: Lin Zhipeng |