CN105237753A - Preparation method of cage-shaped organic silicon hybridized star-shaped polyester soft PVC plasticizer - Google Patents
Preparation method of cage-shaped organic silicon hybridized star-shaped polyester soft PVC plasticizer Download PDFInfo
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- CN105237753A CN105237753A CN201510782348.5A CN201510782348A CN105237753A CN 105237753 A CN105237753 A CN 105237753A CN 201510782348 A CN201510782348 A CN 201510782348A CN 105237753 A CN105237753 A CN 105237753A
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Abstract
The invention relates to the technical fields of the preparation and modification of functional macro-molecular materials, and particularly relates to a preparation method of a cage-shaped organic silicon hybridized star-shaped polyester soft PVC plasticizer. The preparation method comprises the following steps: (1) sequentially cracking oxidizing and hydrogenating ricinoleic acid to obtain a mixed product of dihydric alcohol and nonanol acid; (2) facilitating esterolysis reaction of an apex group of 8-methacryloxypropyl cage-shaped silsesquioxane to obtain 8-propanol cage-shaped silsesquioxane; (3) mixing the mixed product obtained in the step (1) and the 8-methacryloxypropyl cage-shaped silsesquioxane obtained in the step (2) with a dimer acid according to a mass ratio to obtain a mixed solution; and (4) adding an esterification catalyst and a dehydration agent into the mixed solution prepared in the step (3), and refluxing to obtain the cage-shaped organic silicon hybridized star-shaped polyester soft PVC plasticizer. The plasticizer has excellent application performance and is high in migration resistance, solvent resistant effect, weather resistance and the like.
Description
Technical field
The present invention relates to the technical field of functional high molecule material preparation and modification, be specifically related to the preparation method of a kind of cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.
Background technology
Polyvinyl chloride (PVC) is one of synthetical resin products that output is maximum in the world.In polyvinyl chloride (PVC) RESINS, add appropriate softening agent, can be made into multiple boardy product and soft goods.Wherein, flexible PVC goods account for 30% of the PVC market share, and it is widely used in manufacturing imitation leather, packaging material for food, electric wire and toy for children etc.The softening agent used in flexible PVC is phthalic acid two (2-ethyl) own ester (DEHP) mainly, it have good with PVC consistency, plasticizing efficiency is high, cheap, the plurality of advantages such as security and electrical insulating property that do not affect goods.But because DEHP is small-molecule substance, and and there is no chemical bonding between PVC, its addition is usual up to 30wt% ~ 50wt% again, and therefore DEHP easily moves in external agency, makes the performance degradation of goods, causes environmental pollution simultaneously.At the Sensitive Domain such as medicine equipment and toy for children, the migration of DEHP also can be detrimental to health.In addition, some flexible PVCs, when extremely frigid zones uses, require that it has good low-temperature impact resistance.Common softening agent under cryogenic, can move out from PVC matrix, loses plasticization effect.Therefore, the problem that plasticizer migration brings causes the extensive concern of people, urgently to be resolved hurrily.
Cage-type silsesquioxane (POSS) spatially has three polyhedral structures, is made up of inorganic " core " and organic " drift angle ".Kernel chemical constitution skeleton symbol is (SiO
3/2)
n(n=6,8,10,12 etc.), each Siliciumatom drift angle connects organic group, is hybrid systems in organic-inorganic molecule.The chemical group of drift angle has reactive behavior, can with physics or chemical action mode and polymer formation POSS base nano hybrid composite material.Its hybrid material integrates organic and excellent properties that is inorganic materials, and its thermomechanical property, mechanical property, electric property and magnetic etc. are obtained for great improvement.
Ricinolic acid is hydrolyzed by Viscotrol C and obtains, and Viscotrol C itself industrially has a lot of purposes.Pure Viscotrol C can be used for medicine industry, and what quality was more secondary can be made into turkey red oil, for dyeing and weaving industry.Paint and lube stock can also be used as in addition.Multiple useful Chemicals can be obtained, as nonane diacid, suberic acid, sebacic acid, methyln-hexyl ketone, 2-sec-octyl alcohol, enanthaldehyde, undecylenic acid etc. after ricinolic acid cracking.
Dimeracid refers to the unsaturated fatty acids of the linolic acid of the natural fats and oils straight chain that is main ingredient or unsaturated fatty acid ester under clay catalytic effect, by the dimer of self polycondensation such as Diels-Alder cycloaddition reaction.It is the mixture of multiple isomer, and wherein main component is the monomer of dimer, a small amount of tripolymer or polymer and traces of unreacted.Dimeracid is a kind of important grease chemical article, is used widely in industry such as coating, tensio-active agent, lubricant, printing-ink, hot melt adhesives.
Polyester plasticizer belongs to the category of superpolymer, is characterized in that the volume of molecule is greater than the volume of monomeric plastizer agent molecule, and relative molecular mass is comparatively large, makes the agent of various plastic product post-plasticization not easily therefrom move out when adding in polyvinyl chloride resin as softening agent.Therefore, the character that polyester plasticizer can make PVC plastic goods have some special, these special character determine plastics test piece prepared therefrom and have excellent application performance, as resistance to migration is strong, solvent resistant effect is excellent, weathering resistance is strong.
Summary of the invention
The object of the invention is to solve for the consistency increasing flexible PVC softening agent and matrix, the problem that prevents plasticizer migration, strengthen its low-temperature impact resistance, the method of raw material by chemical modification is organically combined, prepares a kind of cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.Main raw material(s) natural environmental-protective of the present invention, good with PVC consistency, and environment-friendly high-efficiency, low-temperature impact-resistant performance is good, has a extensive future.The softening agent prepared has excellent application performance, improves the performances such as resistance to migration, solvent resistant effect, weathering resistance.
To achieve these goals, the preparation method of a kind of cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent, its preparation process is followed successively by:
S1, ricinolic acid carry out pyrolysis oxidization, hydrogenation reaction successively, obtain the mix products of dibasic alcohol and nonyl alcohol acid, and described dibasic alcohol is 1,3-dihydroxyl nonanediol;
The drift angle group generation ester hydrolysis reaction of S2, prestox acryloxypropyl cage-type silsesquioxane, stirring and refluxing reaction 2 ~ 4h, obtains eight propyl alcohol base cage-type silsesquioxanes;
The eight propyl alcohol base cage-type silsesquioxanes that S3, the nonyl alcohol acid obtained by step S1 and 1,3-dihydroxyl nonanediol and step S2 obtain, mix in mass ratio with dimeracid, obtained mixed solution;
Add catalyst for esterification reaction and dewatering agent, back flow reaction 2 ~ 6h in S4, the mixed solution prepared in step S3, obtain cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.
Further, in described step S1, the method for pyrolysis oxidization is the one in ozone oxidation, peroxide oxidation, nitric acid oxidation, atmospheric oxidation, the oxidation of ruthenium salt, cobalt salt oxidation, hypochlorite oxidation or biochemical oxidation.
Further, in described step S1, the catalyzer of hydrogenation reaction is the one in Ni series catalysts, Pt series catalysts or palladium series catalyst.
Preferably, described Ni series catalysts is Renay-Ni catalyzer; Described palladium series catalyst is Pd/C catalyzer.
Further, in described step S2, the catalyzer of ester hydrolysis reaction is the one in acidic aqueous solution or alkaline aqueous solution.
Preferably, described acidic aqueous solution is aqueous sulfuric acid, and described alkaline aqueous solution is aqueous sodium hydroxide solution.
Further, nonyl alcohol acid and 1,3-dihydroxyl nonanediol in described step S3: eight propyl alcohol base cage-type silsesquioxanes: the mass ratio of dimeracid is 70 ~ 80:10 ~ 20:10 ~ 20.
Further, the catalyst for esterification reaction in described step S4 is the one in general acid type catalyst, solid acid catalyst or heteropolyacid catalyst; Dewatering agent in described step S4 is DCC(dicyclohexylcarbodiimide), DIC(N, N'-DIC), EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride) with DMAP(4-Dimethylamino pyridine) in one.
Preferably, described catalyst for esterification reaction is heteropolyacid PW
12/ SiO
2.
Beneficial effect of the present invention:
(1) the cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent that prepared by the present invention adds the consistency of softening agent and matrix, prevents plasticizer migration, strengthens its low-temperature impact resistance.
(2) the cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent that prepared by the present invention has non-volatility, nonmigratory, the feature good with PVC consistency.
(3) the cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent that prepared by the present invention part can replace traditional catalyst, remarkable in economical benefits even completely.
(4) the method condition preparing cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent disclosed by the invention is easily implemented, and preparation technology is comparatively simple, easy to operate, is suitable for promoting.
Accompanying drawing explanation
Fig. 1 is ricinoleic acid molecules structure iron;
Fig. 2 is prestox acryloxypropyl cage-type silsesquioxane molecular structure;
Fig. 3 is dimeracid molecular structure;
Fig. 4 is cage modle organic-silicon hybridization of the present invention star-like polyester flexible PVC softening agent synthesis schematic diagram.
Embodiment
Following preparation method's composition graphs 1-4 elaborates to embodiments of the present invention.It is emphasized that following explanation is only exemplary, instead of in order to limit the scope of the invention and apply.
Embodiment 1
A preparation method for cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent, its preparation process is followed successively by:
S1, ricinolic acid carry out pyrolysis oxidization, Renay-Ni catalytic hydrogenation reaction by ozone oxidation successively, obtain nonyl alcohol acid and 1,3-dihydroxyl nonanediol;
There is ester hydrolysis reaction in the drift angle group of S2, prestox acryloxypropyl cage-type silsesquioxane, stirring and refluxing reaction 4h, obtains eight propyl alcohol base cage-type silsesquioxanes in aqueous sulfuric acid;
The eight propyl alcohol base cage-type silsesquioxanes that S3, the nonyl alcohol acid obtained by step S1 and 1,3-dihydroxyl nonanediol and step S2 obtain, with dimeracid in mass ratio for 70:10:20 mixes, obtained mixed solution;
Catalyst for esterification reaction heteropolyacid PW is added in S4, the mixed solution prepared in step S3
12/ SiO
2and dewatering agent DCC, back flow reaction 2 ~ 6h, obtain cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.
The method that present invention provides pyrolysis oxidization in step S1 is the situation of ozone oxidation, certainly, the method for pyrolysis oxidization can also be any one in peroxide oxidation, nitric acid oxidation, atmospheric oxidation, the oxidation of ruthenium salt, cobalt salt oxidation, hypochlorite oxidation or biochemical oxidation in step S1 on this basis.
Embodiment 2
A preparation method for cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent, its preparation process is followed successively by:
S1, ricinolic acid carry out pyrolysis oxidization, Pd/C catalytic hydrogenation reaction by ozone oxidation successively, obtain nonyl alcohol acid and 1,3-dihydroxyl nonanediol;
There is ester hydrolysis reaction in the drift angle group of S2, prestox acryloxypropyl cage-type silsesquioxane, stirring and refluxing reaction 2h, obtains eight propyl alcohol base cage-type silsesquioxanes in aqueous sodium hydroxide solution;
The eight propyl alcohol base cage-type silsesquioxanes that S3, the nonyl alcohol acid obtained by step S1 and 1,3-dihydroxyl nonanediol and step S2 obtain, with dimeracid in mass ratio for 70:20:10 mixes, obtained mixed solution;
Catalyst for esterification reaction heteropolyacid PW is added in S4, the mixed solution prepared in step S3
12/ SiO
2and dewatering agent DCC, back flow reaction 2 ~ 6h, obtain cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.
Embodiment 3
A preparation method for cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent, its preparation process is followed successively by:
S1, ricinolic acid carry out pyrolysis oxidization, Pd/C catalytic hydrogenation reaction by ozone oxidation successively, obtain nonyl alcohol acid and 1,3-dihydroxyl nonanediol;
There is ester hydrolysis reaction in the drift angle group of S2, prestox acryloxypropyl cage-type silsesquioxane, stirring and refluxing reaction 4h, obtains eight propyl alcohol base cage-type silsesquioxanes in aqueous sulfuric acid;
The eight propyl alcohol base cage-type silsesquioxanes that S3, the nonyl alcohol acid obtained by step S1 and 1,3-dihydroxyl nonanediol and step S2 obtain, with dimeracid in mass ratio for 80:10:10 mixes, obtained mixed solution;
Catalyst for esterification reaction heteropolyacid PW is added in S4, the mixed solution prepared in step S3
12/ SiO
2and dewatering agent DCC, back flow reaction 2 ~ 6h, obtain cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.
Embodiment 4
A preparation method for cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent, its preparation process is followed successively by:
S1, ricinolic acid carry out pyrolysis oxidization, Pd/C catalytic hydrogenation reaction by ozone oxidation successively, obtain nonyl alcohol acid and 1,3-dihydroxyl nonanediol;
There is ester hydrolysis reaction in the drift angle group of S2, prestox acryloxypropyl cage-type silsesquioxane, stirring and refluxing reaction 4h, obtains eight propyl alcohol base cage-type silsesquioxanes in aqueous sulfuric acid;
The eight propyl alcohol base cage-type silsesquioxanes that S3, the nonyl alcohol acid obtained by step S1 and 1,3-dihydroxyl nonanediol and step S2 obtain, with dimeracid in mass ratio for 70:10:20 mixes, obtained mixed solution;
Catalyst for esterification reaction heteropolyacid PW is added in S4, the mixed solution prepared in step S3
12/ SiO
2and dewatering agent DIC, back flow reaction 2 ~ 6h, obtain cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.
The catalyzer that present invention provides hydrogenation reaction in step S1 is the situation of Ni series catalysts and palladium series catalyst, and certainly, in step S1, the catalyzer of hydrogenation reaction can also be Pt series catalysts on this basis.
Equally, the catalyst for esterification reaction that present invention provides in step S4 is heteropolyacid catalyst, dewatering agent in step S4 is the situation of DCC and DIC, certainly, catalyst for esterification reaction on this basis in step S4 can also be general acid type catalyst or solid acid catalyst, and the dewatering agent in step S4 can also be EDC or DMAP.
Last it is noted that obviously, above-described embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of amplifying out or variation be still among protection scope of the present invention.
Claims (9)
1. a preparation method for cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent, is characterized in that, its preparation process is followed successively by:
S1, ricinolic acid carry out pyrolysis oxidization, hydrogenation reaction successively, obtain the mix products of dibasic alcohol and nonyl alcohol acid, and described dibasic alcohol is 1,3-dihydroxyl nonanediol;
The drift angle group generation ester hydrolysis reaction of S2, prestox acryloxypropyl cage-type silsesquioxane, stirring and refluxing reaction 2 ~ 4h, obtains eight propyl alcohol base cage-type silsesquioxanes;
The eight propyl alcohol base cage-type silsesquioxanes that S3, the nonyl alcohol acid obtained by step S1 and 1,3-dihydroxyl nonanediol and step S2 obtain, mix in mass ratio with dimeracid, obtained mixed solution;
Add catalyst for esterification reaction and dewatering agent, back flow reaction 2 ~ 6h in S4, the mixed solution prepared in step S3, obtain cage modle organic-silicon hybridization star-like polyester flexible PVC softening agent.
2. the preparation method of cage modle organic-silicon hybridization according to claim 1 star-like polyester flexible PVC softening agent, it is characterized in that, in described step S1, the method for pyrolysis oxidization is the one in ozone oxidation, peroxide oxidation, nitric acid oxidation, atmospheric oxidation, the oxidation of ruthenium salt, cobalt salt oxidation, hypochlorite oxidation or biochemical oxidation.
3. the preparation method of cage modle organic-silicon hybridization according to claim 1 star-like polyester flexible PVC softening agent, is characterized in that, in described step S1, the catalyzer of hydrogenation reaction is the one in Ni series catalysts, Pt series catalysts or palladium series catalyst.
4. the preparation method of cage modle organic-silicon hybridization according to claim 1 star-like polyester flexible PVC softening agent, is characterized in that, described Ni series catalysts is Renay-Ni catalyzer; Described palladium series catalyst is Pd/C catalyzer.
5. the preparation method of cage modle organic-silicon hybridization according to claim 1 star-like polyester flexible PVC softening agent, is characterized in that, in described step S2, the catalyzer of ester hydrolysis reaction is the one in acidic aqueous solution or alkaline aqueous solution.
6. the preparation method of cage modle organic-silicon hybridization according to claim 5 star-like polyester flexible PVC softening agent, is characterized in that, described acidic aqueous solution is aqueous sulfuric acid, and described alkaline aqueous solution is aqueous sodium hydroxide solution.
7. the preparation method of cage modle organic-silicon hybridization according to claim 1 star-like polyester flexible PVC softening agent, it is characterized in that, nonyl alcohol acid and 1,3-dihydroxyl nonanediol in described step S3: eight propyl alcohol base cage-type silsesquioxanes: the mass ratio of dimeracid is 70 ~ 80:10 ~ 20:10 ~ 20.
8. the preparation method of cage modle organic-silicon hybridization according to claim 1 star-like polyester flexible PVC softening agent, it is characterized in that, the catalyst for esterification reaction in described step S4 is the one in general acid type catalyst, solid acid catalyst or heteropolyacid catalyst; Dewatering agent in described step S4 is the one in DCC, DIC, EDC or DMAP.
9. the preparation method of cage modle organic-silicon hybridization according to claim 8 star-like polyester flexible PVC softening agent, is characterized in that, described catalyst for esterification reaction is heteropolyacid PW
12/ SiO
2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250422A (en) * | 2018-01-26 | 2018-07-06 | 青岛科技大学 | A kind of preparation method of organosilicon modified polyester plasticizer |
| CN112920409A (en) * | 2021-01-21 | 2021-06-08 | 成都思立可科技有限公司 | Star-shaped polyester modified siloxane copolymer and preparation method thereof |
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| CN102977350A (en) * | 2012-11-27 | 2013-03-20 | 杭州吉华高分子材料有限公司 | Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin |
| CN103059246A (en) * | 2012-12-18 | 2013-04-24 | 中科院广州化学有限公司 | Silicon hybrid waterborne polyurethane derived from natural fatty acid and preparation method for waterborne polyurethane |
| US20140106274A1 (en) * | 2012-10-14 | 2014-04-17 | Xerox Corporation | Polyhedral oligomeric silsesquioxane toner resins |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140106274A1 (en) * | 2012-10-14 | 2014-04-17 | Xerox Corporation | Polyhedral oligomeric silsesquioxane toner resins |
| CN102977350A (en) * | 2012-11-27 | 2013-03-20 | 杭州吉华高分子材料有限公司 | Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin |
| CN103059246A (en) * | 2012-12-18 | 2013-04-24 | 中科院广州化学有限公司 | Silicon hybrid waterborne polyurethane derived from natural fatty acid and preparation method for waterborne polyurethane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250422A (en) * | 2018-01-26 | 2018-07-06 | 青岛科技大学 | A kind of preparation method of organosilicon modified polyester plasticizer |
| CN108250422B (en) * | 2018-01-26 | 2020-04-03 | 青岛科技大学 | Preparation method of organic silicon modified polyester plasticizer |
| CN112920409A (en) * | 2021-01-21 | 2021-06-08 | 成都思立可科技有限公司 | Star-shaped polyester modified siloxane copolymer and preparation method thereof |
| CN112920409B (en) * | 2021-01-21 | 2022-02-15 | 成都思立可科技有限公司 | Star-shaped polyester modified siloxane copolymer and preparation method thereof |
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Address after: 515559 Guangdong County of Jiedong province Jieyang Paotai town Kengzi in Pai Patentee after: Guangdong Dahua ecological science and Technology Co Ltd Address before: 515559 Guangdong County of Jiedong province Jieyang Paotai town Kengzi in Pai Patentee before: GUANGDONG DAHUA WATER SAVING TECHNOLOGY CO., LTD. |