CN101775125A - Non-aromatic nucleus structure poly-hexahydrobenzene phthalic anhydride dihydric alcohol ester plasticizer and preparation method thereof - Google Patents
Non-aromatic nucleus structure poly-hexahydrobenzene phthalic anhydride dihydric alcohol ester plasticizer and preparation method thereof Download PDFInfo
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- CN101775125A CN101775125A CN201010110558A CN201010110558A CN101775125A CN 101775125 A CN101775125 A CN 101775125A CN 201010110558 A CN201010110558 A CN 201010110558A CN 201010110558 A CN201010110558 A CN 201010110558A CN 101775125 A CN101775125 A CN 101775125A
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Abstract
The invention relates to non-aromatic nucleus structure poly-hexahydrobenzene phthalic anhydride dihydric alcohol ester plasticizer and a preparation method thereof, belonging to the technical field of the synthesis of low molecular weight polyester compounds of fine chemicals. The invention is prepared by esterifying and polymerizing hexahydrobenzene with dihydric alcohol and n-butyl alcohol with the existing of homogeneous phase composite complex catalyst tetrabutyl titanate or tetraisopropyl titanate catalyst under 140-200 DEG C. The invention meets the requirements of energy conservation and cleaner production, and the prepared product of poly-hexahydrobenzene phthalic anhydride dihydric alcohol ester plasticizer is a novel polyester plasticizer with the characteristics of good compatibility with high polymer material and anti-migratory performance; the polyester plasticizer has the excellent characteristics of good resist-extraction performance, light color, good thermostability and fundamental innocuous performance; the invention is particularly suitable for environmental protection polyvinyl chloride (PVC) plastic product, medical plastic, refrigerator sealing strip, environmental protection PVC cable sheath and can be used as environmental protection assist agent of functional high polymer material for meeting the requirements of oil resistance and anti-migratory performance.
Description
Technical field
A kind of poly-HHPA binary alcohol esters softening agent and preparation method thereof, by the synthetic resistance to migration of no aromatic ring structure diprotic acid and polyol reaction, with excellent polyester plasticizer of PVC material compatibility and preparation method thereof.The synthetic technical field of low-molecular-weight polyester compound that relates to fine chemicals.Specifically, relate to a kind ofly have that the extractable of anti-the solvent is good, product colour is shallow, the compound of the poly-HHPA binary alcohol esters of Heat stability is good, environment-protecting asepsis, can be used as environment-friendly polyvinyl chloride (PVC) plastics, medical plastic, refrigerator sealed strip, environment-friendly PVC cable sheath and answer used additives as oil resistant and the functional high molecule material that anti-migration requires.
Background technology
Softening agent is that a class is used maximum additives for plasticss, is one of important fine chemical product, and the mechanical characteristics of improving goods such as plastics, rubber and macromolecular material is had crucial effect.About about 90% based on O-phthalic acid type monomer ester, as dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), phthalic acid fourth-benzyl ester etc. in the domestic and international softening agent Industrial products.
Because the ester compound molecular weight ratio of haplotype is lower, relatively poor with the consistency of macromolecular material, therefore the PVC goods are extracted out by oils or organic solvent in use and production process easily, influenced the application performance of functional high molecule material goods, this class problem mainly is presented as: rubber on the automobile and decorative plastic material in use can occur because plasticizer exudation causes " perspiration " phenomenon, come off thereby make rubber cracking occur; In electric wire, oozing out of softening agent will cause outsourcing ageing of plastics cracking; Plastic Packaging Materials is because above-mentioned factor can't be at its surface seal literal, in addition, be used for the goods that oil well etc. need be dipped in oils, anti-extractable for softening agent in the plastics will have higher requirement, polyester plasticizer of the present invention is as having certain polymerization degree and molecular weight, aggretion type ester analog assistant that anti-extractable is good, and do not have aromatic ring structure in its molecular structure.
New plasticizer as excellent performance, the higher polyester plasticizer of molecular weight has purposes widely. and the molecular weight of polyester plasticizer and PVC are comparatively approaching, have consistency preferably with the PVC material, and toxicity is low, volatility is low, anti-extraction and resistance to migration can be good.Because its good comprehensive performances, polyester plasticizer is widely used in various goods such as acrylic rubber goods, epichlorohydrin rubber goods, exterior-coated nitrile rubber article, PVC oil resistant cable, coal gas sebific duct, waterproof roll, leatheroid, toy for children, beverage flexible pipe, milk-product machinery and Bottle cap spacer, the indoor flawless finish product of automobile.Special when the PVC goods need keep distinctive chemical property and under oil, fat or emulsion effect anti-migration use the polyphosphazene polymer ester plasticizer often, when polyester plasticizer is used for rubber item, can make rubber have sulfuration thermotolerance, oil-proofness, anti swelling and resistance to migration, can improve the sizing material process industrial art performance again, in EVA-VC graft copolymerization resin, polyester plasticizer can be used as hard properties-correcting agent and uses.
Because there is the dispute of toxicity problem in phthalic ester plasticizer, cause some Application Areass of many traditional phthalate primary plasticizers to be restricted, as studies show that DOP, may there be the potential carcinogenic danger in phthalic ester plasticizers such as DBP, mainly be in its molecular structure, to contain to contain phenyl ring in the bis phthalate structure and have and carcinogenic may become the point at issue, a lot of countries have taked corresponding restriction, FDA (FDA), European Union etc. have forbidden that this type of softening agent is applied to food product pack, the plastics that makeup and toy for children etc. and human body contact closely.
Summary of the invention
The object of the invention is to provide in a kind of molecular structure does not have phenyl ring, and petchem with certain molecular weight, in the presence of composite catalyst, use HHPA and polyvalent alcohol synthesizing polyester softening agent and preparation method thereof, overcome little, the easy volatilization of monomeric ester compounds molecular weight, in the PVC goods, be easy to generate the shortcoming of migration, provide have that anti-extractable is good, the poly-HHPA dibasic alcohol polyester plasticizer and the synthetic method thereof of good insulation preformance, Heat stability is good, make the resultant of reaction can many-sided application in functional high molecule material.
Technical scheme of the present invention: a kind of poly-HHPA glycol ether ester plasticizer is that feedstock production gets with HHPA, glycol ether, compound complex catalyst and end-capping reagent monohydroxy-alcohol, and reaction equation is:
The product structure formula is as follows
n＝50-70。
The preparation method of described poly-HHPA glycol ether ester plasticizer, with HHPA, glycol ether, compound complex catalyst and end-capping reagent monohydroxy-alcohol are raw material, with the hexanaphthene is the band aqua, the reaction feed ratio is that the mol ratio of HHPA and glycol ether is 1.05-1.10: 1, the mol ratio of end-capping reagent monohydroxy-alcohol and HHPA is 0.10: 1, the mole dosage of compound complex catalyst is 1 ‰ of a HHPA mole dosage-5 ‰, heated and stirred under the normal pressure. be warmed up to 140 ℃ and pick up counting, heat up then, 190 ℃-200 ℃ of highest response warm areas, after being warmed up to 140 ℃ of reaction 5～6h that pick up counting, cold slightly, underpressure distillation, and with water vapor and nitrogen bubble, be decompressed to residual voltage 0.04Mpa～0.096Mpa gradually, intensification steams low molecular weight impurities, stops decompression when no overhead product, cooling, filter, leach liquid and be poly-HHPA glycol ether ester product;
Described compound complex catalyst is selected tetrabutyl titanate or titanium isopropylate for use, and described end-capping reagent monohydroxy-alcohol is selected propyl carbinol or isopropylcarbinol for use.
The raw material of polyreaction of the present invention also comprises the aliphatic dibasic acids that does not contain adjacent phenylbenzene functional group, and wherein, organic dibasic acid comprises propanedioic acid, Succinic Acid, hexanodioic acid and sebacic acid; Dibasic alcohol comprises, propylene glycol, 1,3 butyleneglycol, 1,4 butyleneglycol, glycol ether, Diethylene Glycol; End-capping reagent comprises, propyl carbinol, isopropylcarbinol, 2-Ethylhexyl Alcohol, isooctyl alcohol, different alcohol.
Beneficial effect of the present invention: in the molecular structure unit of polyester plasticizer of the present invention, the raw material that does not contain phthalic acid can effectively reach the minimum and entire reaction course of good product performance, particularly transport property and need not neutralize, wash, do not have " three wastes " to produce, reach the effect of energy-saving and emission-reduction.
The cyclohexane polycarboxylic acid polymkeric substance that the present invention is obtained, can be used as environment-friendly plasticizer uses, particularly the finished product of this softening agent, quality and processing rerum natura are all suitable with traditional adjacent benzene class series softening agent, can not produce harm to organism and environment, so can replace traditional adjacent benzene class series softening agent.
Description of drawings
Fig. 1 HHPA gathers glycol ether ester product infrared spectrogram.
Embodiment
Below, enumerate the advantage that embodiment and comparative example are further illustrated technology contents of the present invention, but interest field of the present invention is not only limited to the scope of embodiment.
Embodiment 1:
In reactor, drop into HHPA, glycol ether, propyl carbinol, catalyzer metatitanic acid four butyl esters/titanium isopropylate and band aqua hexanaphthene and activated carbon raw material in proportion, wherein: the mol ratio of HHPA and glycol ether is 1.10: 1, the mol ratio of propyl carbinol and HHPA is 0.10: 1, and tetrabutyl titanate/titanium isopropylate add-on is 1 ‰ of a feed molar consumption (in the HHPA molar weight).At first in system, feed nitrogen 20min, so that drive air away, heated and stirred under the normal pressure. be warmed up to 140 ℃ and pick up counting, heat up then, 190 ℃-200 ℃ of highest response warm areas, after being warmed up to 140 ℃ of reaction 5～6h that pick up counting, cold slightly, system is switched to the decompression reaction, with being decompressed to residual voltage 0.04Mpa under water vapor and the nitrogen bubble gradually, intensification steams low-molecular weight compound and small amount of impurities, stops decompression when no overhead product, and liquid promptly obtains poly-HHPA glycol ether ester plasticizer product in the cooled and filtered reactor slightly.The product infrared spectrogram as shown in Figure 1,3500cm wherein
-1Place's product has more weak hydroxyl absorption peak, is that the hydroxyl of an end of dibasic alcohol does not dissociate out with carboxyl esterification or unreacted alcohol does not steam.2943～2861cm
-1It is the C-H stretching vibration absorption peak of methyl and methylene radical.1732cm
-1The ester carbonyl stretching vibration absorption peak at place, 1170cm
-1About ester C-O stretching vibration absorption peak, illustrating has polyester construction in the product, and does not have the phenyl ring absorption peak occur in the fingerprint region.Yield is 97.5%, product main characteristic physical data tabulation 1.
The characteristic of the poly-HHPA glycol ether ester plasticizer product of table 1
| Lot identification mark | ??1 | ??2 | ??3 |
| Mode of appearance | Transparent oily liquid | Transparent oily liquid | Transparent oily liquid |
| Colourity (platinum-cobalt)/number | ??50 | ??80 | ??30 |
| Initial acid number/(mgKOHg -1) | ??419.55 | ??418.00 | ??418.48 |
| Product acid number/(mgKOHg -1) | ??0.14 | ??0.12 | ??0.13 |
| The esterification degree of depth/% | ??99.85 | ??99.89 | ??99.87 |
| Saponification value/(mgKOHg -1) | ??514 | ??509 | ??522 |
Embodiment 2:
In reactor, drop into HHPA in proportion, glycol ether, isopropylcarbinol, catalyzer metatitanic acid four butyl esters/titanium isopropylate and band aqua hexanaphthene and activated carbon raw material, wherein: the mol ratio of HHPA and glycol ether is 1.10: 1, the mol ratio of isopropylcarbinol and HHPA is 0.10: 1, tetrabutyl titanate/titanium isopropylate add-on is 5 ‰ of a feed molar consumption (in the HHPA molar weight). at first in system, feed nitrogen 20min, so that drive air away, heated and stirred under the normal pressure. be warmed up to 140 ℃ and pick up counting, heat up then, 190 ℃-200 ℃ of highest response warm areas, after being warmed up to 140 ℃ of reaction 5～6h that pick up counting, cold slightly, system is switched to the decompression reaction, with being decompressed to residual voltage 0.096Mpa under water vapor and the nitrogen bubble gradually, intensification steams low-molecular weight compound and small amount of impurities, when no overhead product, stop decompression, liquid promptly obtains poly-HHPA glycol ether ester plasticizer product in the cooled and filtered reactor slightly, product yield is 98.3%, color and luster 50 (platinum-cobalt), acid value 0.08mgKOHg
-1
Comparative example 1-2:
Reactant ratio and processing condition are with embodiment 1, the catalyst system therefor difference, and the related data such as the table 2 of comparative product are listed.
Table 2 embodiment and comparative example related data are relatively
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | |
| Catalyst type | Sulfuric acid (98%) | Sad high tin | Tetrabutyl titanate/titanium isopropylate 1 ‰ | Tetrabutyl titanate/titanium isopropylate 5 ‰ |
| Product acid number/(mgKOHg -1) | ??1.25 | ??0.25 | ??0.12 | ??0.08 |
| Color and luster (platinum-cobalt) | ??200 | ??120 | ??80 | ??50 |
| Reaction times (h) | ??6.5 | ??6.0 | ??6.0 | ??6.0 |
| Product yield (%) | ??90.5 | ??93.5 | ??97.5 | ??98.3 |
Claims (2)
1. a poly-HHPA glycol ether ester plasticizer is characterized in that with HHPA, glycol ether, compound complex catalyst and end-capping reagent monohydroxy-alcohol being that feedstock production gets, and its structural formula is as follows:
n＝50-70。
2. the preparation method of the described poly-HHPA glycol ether ester plasticizer of claim 1, it is characterized in that with HHPA, glycol ether, compound complex catalyst and end-capping reagent monohydroxy-alcohol are raw material, with the hexanaphthene is the band aqua, the reaction feed ratio is that the mol ratio of HHPA and glycol ether is 1.05-1.10: 1, the mol ratio of end-capping reagent monohydroxy-alcohol and HHPA is 0.10: 1, the mole dosage of compound complex catalyst is 1 ‰ of a HHPA mole dosage-5 ‰, heated and stirred under the normal pressure. be warmed up to 140 ℃ and pick up counting, heat up then, 190 ℃-200 ℃ of highest response warm areas, after being warmed up to 140 ℃ of reaction 5～6h that pick up counting, cold slightly, underpressure distillation, and with water vapor and nitrogen bubble, be decompressed to residual voltage 0.04Mpa～0.096Mpa gradually, intensification steams low molecular weight impurities, stops decompression when no overhead product, cooling, filter, leach liquid and be poly-HHPA glycol ether ester product;
Described compound complex catalyst is selected tetrabutyl titanate or titanium isopropylate for use;
Described end-capping reagent monohydroxy-alcohol is selected propyl carbinol or isopropylcarbinol for use.
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| CN102391482A (en) * | 2011-09-13 | 2012-03-28 | 江南大学 | Non-toxic environmentally friendly nadic anhydride polyester plasticizer and preparation method thereof |
| CN103242516A (en) * | 2013-05-23 | 2013-08-14 | 江南大学 | Preparation method of glyceryl polyester used as PVC (Polyvinyl Chloride) plasticizer |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
| KR20150043284A (en) * | 2012-08-16 | 2015-04-22 | 디아이씨 가부시끼가이샤 | Modifying agent for cellulose ester resins, cellulose ester optical film, and protective film for polarizing plates |
| CN108948426A (en) * | 2018-07-05 | 2018-12-07 | 胡果青 | A kind of preparation method of plastic plasticizer |
| CN109867930A (en) * | 2019-02-20 | 2019-06-11 | 朱海鹏 | Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof |
| WO2022146062A1 (en) * | 2020-12-30 | 2022-07-07 | 한화솔루션 주식회사 | Ester-based plasticizer composition and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2621530B2 (en) * | 1990-01-24 | 1997-06-18 | 東洋紡績株式会社 | Paint composition for painted steel plate |
| DE10054504A1 (en) * | 2000-11-03 | 2002-05-16 | Alfred Krueger | Production of high-molecular weight cyclic dicarboxylic acid for use e.g. in epoxy coating material, involves reacting diacid anhydride with diol to form a half-ester and then reacting with more anhydride, using a cyclic reactant |
| EP1553148A1 (en) * | 2004-01-09 | 2005-07-13 | Surface Specialties, S.A. | Powder coating compositions |
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| CN102391482A (en) * | 2011-09-13 | 2012-03-28 | 江南大学 | Non-toxic environmentally friendly nadic anhydride polyester plasticizer and preparation method thereof |
| CN102391482B (en) * | 2011-09-13 | 2013-01-23 | 江南大学 | Non-toxic environmentally friendly nadic anhydride polyester plasticizer and preparation method thereof |
| KR20150043284A (en) * | 2012-08-16 | 2015-04-22 | 디아이씨 가부시끼가이샤 | Modifying agent for cellulose ester resins, cellulose ester optical film, and protective film for polarizing plates |
| CN104603174A (en) * | 2012-08-16 | 2015-05-06 | Dic株式会社 | Modifying agent for cellulose ester resins, cellulose ester optical film, and protective film for polarizing plates |
| CN104603174B (en) * | 2012-08-16 | 2017-09-22 | Dic株式会社 | Cellulose ester resin is with modifying agent, cellulose esters optical thin film and Polarizer diaphragm |
| TWI619740B (en) * | 2012-08-16 | 2018-04-01 | 迪愛生股份有限公司 | Cellulose ester resin composition, cellulose ester optical film and polarizing plate protective film |
| KR102075996B1 (en) * | 2012-08-16 | 2020-02-11 | 디아이씨 가부시끼가이샤 | Modifying agent for cellulose ester resins, cellulose ester optical film, and protective film for polarizing plates |
| CN103242516A (en) * | 2013-05-23 | 2013-08-14 | 江南大学 | Preparation method of glyceryl polyester used as PVC (Polyvinyl Chloride) plasticizer |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
| CN108948426A (en) * | 2018-07-05 | 2018-12-07 | 胡果青 | A kind of preparation method of plastic plasticizer |
| CN109867930A (en) * | 2019-02-20 | 2019-06-11 | 朱海鹏 | Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof |
| WO2022146062A1 (en) * | 2020-12-30 | 2022-07-07 | 한화솔루션 주식회사 | Ester-based plasticizer composition and use thereof |
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