CN102718690A - Polyvinyl chloride plasticizer and preparation method thereof - Google Patents
Polyvinyl chloride plasticizer and preparation method thereof Download PDFInfo
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- CN102718690A CN102718690A CN2012102120278A CN201210212027A CN102718690A CN 102718690 A CN102718690 A CN 102718690A CN 2012102120278 A CN2012102120278 A CN 2012102120278A CN 201210212027 A CN201210212027 A CN 201210212027A CN 102718690 A CN102718690 A CN 102718690A
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Abstract
The invention belongs to the technical field of a general polymer material, and particularly relates to a polyvinyl chloride plasticizer and a preparation method thereof. Sulfonic acid instead of phthalate is used as a raw material, and mercapto-substituted phthalate is prepared via acyl chlorination, esterification and reduction. When the plasticizer is used, the transformation temperature and flow temperature of PVC (polyvinyl chloride) glass can be reduced, the migration of the plasticizer can be inhibited, and the thermal stability of PVC can be improved. The modified PVC can maintain the stability in a long time, no damage can be caused to the environment, and the scope of application of PVC can be expanded undoubtedly.
Description
Technical field
The invention belongs to commodity polymer material technology field, be specifically related to a kind of plasticizer for polyvinyl chloride and preparation method thereof.
Background technology
SE (PVC) is one of five big general synthetic resins, also is one of plastics variety of realizing the earliest in the world suitability for industrialized production.Because that it has is nonflammable, anticorrosive, wear-resisting, electrical insulating property is good, physical strength is than advantages such as height, is widely used in industries such as industry, agricultural, building, communications and transportation, electric power, telecommunication and packing.PVC whole world output is only second to Vilaterm (PE) at present, occupies second.
Because PVC is a polar molecule, has very strong interaction between the molecular chain, therefore need to add softening agent and reduce the reactive force between the PVC molecular chain, the fusing point of second-order transition temperature, yield temperature and the contained crystallite of PVC plastics is all reduced.Except that the big softening agent of relative molecular weights such as polyester, mostly softening agent is the organic molecule material, and it is added among the PVC, not with the polymerization of PVC molecular chain, and combines with the PVC molecule with hydrogen bond or Van der Waals force, keeps relatively independent chemical property each other.When flexible PVC contacts mounting medium for a long time, during like gas phase, liquid phase, solid-phase media, softening agent will parse from the PVC matrix gradually, moves in the medium.This will cause PVC to lose initial performance gradually; May pollute physiological liquid owing to move to the additive of matrix surface in addition; Like blood, serum or blood plasma etc., so when the PVC goods are being applied on biomedical sector or the toy for children, can cause serious threat to health.Many researchs show that phthalic acid n-octyl DOP meeting toxigenicity and spinoff are especially to animal or human body tissue, like pituitary gland, liver, testis etc.Therefore DOP is forbidden one of phthalic ester plasticizer that is used for child care products and toy product by Consumer Product Safety Commission (CPSC) recently.
Because DOP has developed some and has been used to alleviate softening agent from the method for flexible PVC to environmental transport and transfer the harm of human body, such as using superoxide, azo cpd, sulfide or propenoate carries out surface-treated to the PVC goods.Available in addition γ-radiation or plasma radiation carry out physically modified to the surface.All these methods all are to carry out crosslinkedly to body surface, make additive be blocked in the behind of these " fence ".
In fact, the effective ways of solution migration problem are that additive and polymer molecular chain are formed covalent linkage through chemical reaction.Therefore chlorine among the PVC can be introduced nucleophilic functional group it is grafted on the PVC chain by nucleophilic substitution in the small molecules softening agent.Starnes etc. have proposed utilization aliphatics and aromatic sulfhydryl compound as stablizer, to replace the heavy metallic salt in the original prescription.Their research shows, the organic mercaptan that contains one or more carboxylicesters functions (mercaptan ester) has significant effect as the thermo-stabilizer of SE.
Summary of the invention
The object of the present invention is to provide a kind of plasticizer for polyvinyl chloride and preparation method thereof; This softening agent can be grafted on the PVC chain through chemical reaction easily, thereby reduces PVC molecule interchain polar interaction power, second-order transition temperature and yield temperature.
Plasticizer for polyvinyl chloride provided by the invention, its structure is shown in logical formula I or (II):
The logical formula II of logical formula I
Wherein, R is the aliphatic group of straight or branched:
, n is 2～7 integer.
Said plasticizer for polyvinyl chloride, preferred following compound: 4-sulfydryl n-butyl phthalate, 4-sulfydryl dinoctyl phthalate, 4-sulfydryl dimixo-octyl phthalate, 5-sulfydryl m-phthalic acid di-n-butyl, 5-sulfydryl m-phthalic acid di-n-octyl, 5-sulfydryl diisooctyl isophthalate.
Concrete structure is as follows:
4-sulfydryl n-butyl phthalate 5-sulfydryl m-phthalic acid di-n-butyl
4-sulfydryl dinoctyl phthalate 5-sulfydryl m-phthalic acid di-n-octyl
4-sulfydryl dimixo-octyl phthalate 5-sulfydryl diisooctyl isophthalate
Among the present invention, the preparation method of above-mentioned plasticizer for polyvinyl chloride is following:
(1) dichloro-acetyl substituted benzene SULPHURYL CHLORIDE is synthetic
Sulfonic acid substituted benzene diformate and PCl
5Mix, 170～180 ℃ of heating added solvent after 15～20 hours, continue to stir, and cooling, underpressure distillation obtains dichloro-acetyl substituted benzene SULPHURYL CHLORIDE;
(2) chlorosulfonyl substituted benzene dicarboxylic acid esters is synthetic
Get a step product and mix with solvent, alcohols and organic amine, heated and stirred, after question response finished, reaction solution was used diluted acid respectively, saturated NH
4The Cl aqueous solution and water washing merge organic phase, and be dry, filter, concentrate and obtain chlorosulfonyl substituted benzene dicarboxylic acid esters, and wherein alcohols is the Fatty Alcohol(C12-C14 and C12-C18) of straight or branched, and structural formula is CH
3(CH
2) n CH
2OH, n are 2～7 integer, and said dichloro-acetyl substituted benzene SULPHURYL CHLORIDE is 1:3～1:2 with the mol ratio of alcohol, and the mol ratio of dichloro-acetyl substituted benzene SULPHURYL CHLORIDE and organic amine is 1:3～1:2;
(3) sulfydryl substituted benzene dicarboxylic acid esters is synthetic
Get the product that step 2 obtains and be dissolved in the acetate, add SnCl
2/ HCl reductant solution, heated and stirred finishes to reaction, and organic solvent extraction is used NaHCO then respectively
3Clean with water, organic phase is dry, filter, concentrate bullion, purify through column chromatography for separation again and obtain title product.
Among the present invention, the solvent in the step 1 is a kind of of benzene, toluene or YLENE, said sulfonic acid substituted benzene diformate and PCl
5Mol ratio be 1:3～2:5.Among the present invention, in the step 2, said solvent is chloroform or toluene, and used organic amine is triethylamine or pyridine etc., and Heating temperature is 55～70 ℃, and the reaction times is 1～4h.Among the present invention, in the step 3, Heating temperature is 50～70 ℃, and the reaction times is 8～15h.The organic solvent of aftertreatment extraction is methylene dichloride or chloroform.
Among the present invention, preparing method's reaction equation is shown in the following figure:
This compound method step was compared with former compound method [US6667357, US6747081, US6762231, US6762231], and step is simple, and productive rate and purity all are greatly improved.
The softening agent that the present invention obtains can reduce second-order transition temperature, yield temperature, the inhibition migration of plasticizer of PVC and improve the thermostability of PVC.It is stable for a long time that modified PVC can keep, and also can not damage environment, will expand the range of application of PVC undoubtedly greatly.
Description of drawings
The proton nmr spectra of 4-sulfydryl-dinoctyl phthalate that Fig. 1 obtains for embodiment 3.
The PVC proton nmr spectra of 4-sulfydryl-dinoctyl phthalate modification that Fig. 2 obtains for embodiment 3.
Fig. 3 is the variation diagram of modified PVC second-order transition temperature.
Fig. 4 schemes for plasticizer concentration in the PVC soaking solution over time.
Embodiment
Further specify the present invention with instance below, but protection scope of the present invention is not limited in examples of implementation.Those skilled in the art is also included within the protection domain of the present invention in other variation and the modification of making under the situation that does not deviate from spirit of the present invention and protection domain.
(1) 4-chlorosulfonyl phthalyl chloride is synthetic
Phthalic acid-4-sodium sulfonate 100g is added in the 1L round-bottomed flask, under agitation add 220g PCl
5, 180 ℃ of oil bath heating were reacted 15 hours; In reactor drum, add the 500ml toluene solution then, stop heating, continue to stir.Leave standstill for some time, the NaCl of white separates out, and filters, and underpressure distillation obtains 4-chlorosulfonyl phthalyl chloride.
(2) 4-chlorosulfonyl dimixo-octyl phthalate is synthetic
Get the product 33.2mmol in a step, place the 500ml round-bottomed flask, add 250ml trichloromethane stirring and dissolving, under agitation add 66.4mmol 2-Ethylhexyl Alcohol and 66.4mmol triethylamine successively, 65 ℃ were reacted 2 hours down.The product organic phase is used 1M HCl solution, saturated NH respectively
4Cl solution, and deionized water wash.Merge organic phase then, anhydrous magnesium sulfate drying filters, and concentrates the crude product that obtains and obtains 4-chlorosulfonyl dimixo-octyl phthalate through underpressure distillation.
(3) 4-sulfydryl dimixo-octyl phthalate is synthetic
Get step product 10.2mmol and place the 250ml round-bottomed flask, use the 5.0ml acetate dissolution, 4.6g SnCl
2Be dissolved in and process reductive agent among the 100mlHCl, stir down dropwise dropping, add the back and keep 65 ℃, stopped reaction after 10 hours.With 250ml dichloromethane extraction water for several times, use 1mol/L NaHCO then successively
3, deionized water wash, organic phase is used anhydrous magnesium sulfate drying, filters, and underpressure distillation obtains crude product, again through column chromatography (elutriant: methylene dichloride) separate, obtain 4-sulfydryl dimixo-octyl phthalate.
(1) 5-chlorosulfonyl m-phthaloyl chloride is synthetic
5-sodium sulfo isophthalate 80g is added in the 1L round-bottomed flask, under agitation add 240g PCl
5, reaction is 20 hours under 170 ℃ of oil bath temperature conditions; In reactor drum, add the 500ml toluene solution then, stop heating, continue to stir.Leave standstill for some time, the NaCl of white separates out, and filters, and underpressure distillation obtains 5-chlorosulfonyl m-phthaloyl chloride.
(2) 5-chlorosulfonyl diisooctyl isophthalate is synthetic
Get the product 5-chlorosulfonyl-m-phthaloyl chloride 33.2mmol in a step; Place the 500ml round-bottomed flask; Add 250ml trichloromethane stirring and dissolving, under agitation add 99.6mmol2-ethylhexanol and 99.6mmol triethylamine successively, 55 ℃ were reacted 4 hours down.The product organic phase is used 1mol/l HCl solution, saturated NH successively
4Cl solution, and deionized water wash.Merge organic phase then, anhydrous magnesium sulfate drying filters, and concentrates, and the crude product that obtains obtains 5-chlorosulfonyl diisooctyl isophthalate through underpressure distillation.
(3) 4-sulfydryl dimixo-octyl phthalate is synthetic
Get step product 10.2mmol and place the 250ml round-bottomed flask, use the 5.0ml acetate dissolution, 4.6g SnCl
2Be dissolved among the 100ml HCl and process reductive agent, under agitation dropwise drip, add the back and under 55 ℃ of temperature, reacted 12 hours stopped reaction.With 250ml dichloromethane extraction water 4 times, use 1mol/L NaHCO then successively
3Washing, deionized water wash, organic phase is used anhydrous magnesium sulfate drying, filters, and underpressure distillation obtains crude product, again through column chromatography (elutriant: methylene dichloride) separate, obtain 5-sulfydryl diisooctyl isophthalate.
Embodiment 3
(1) 4-chlorosulfonyl phthalyl chloride is synthetic
This step is with embodiment 1 step (1).
(2) 4-chlorosulfonyl dinoctyl phthalate is synthetic
Get the product 33.2mmol in a step, place the 500ml round-bottomed flask, add 250ml trichloromethane stirring and dissolving, under agitation add 66.4mmol n-Octanol and 66.4mmol pyridine successively, 70 ℃ were reacted 1 hour down.The product organic phase is used 1M HCl solution, saturated NH respectively
4Cl solution, and deionized water wash.Merge organic phase then, anhydrous magnesium sulfate drying filters, and concentrates the crude product that obtains and obtains 4-chlorosulfonyl dinoctyl phthalate through underpressure distillation.
(3) 4-sulfydryl dinoctyl phthalate is synthetic
Get step product 10.2mmol and place the 250ml round-bottomed flask, use the 5.0ml acetate dissolution, 4.6g SnCl
2Be dissolved among the 100ml HCl and process reductive agent, stir down dropwise dropping, add the back and keep 50 ℃, stopped reaction after 15 hours.With 250ml dichloromethane extraction water for several times, use 1mol/L NaHCO then successively
3, the de-ionized washing, organic phase is used anhydrous magnesium sulfate drying, filters, and underpressure distillation obtains crude product, again through column chromatography (elutriant: chloroform) separate, obtain 4-sulfydryl dinoctyl phthalate.
(1) 4-chlorosulfonyl phthalyl chloride is synthetic
This step is with embodiment 1 step (1).
(2) 4-chlorosulfonyl phthalate ester decanoate is synthetic
Get the product 33.2mmol in a step, place the 500ml round-bottomed flask, add 250ml trichloromethane stirring and dissolving, under agitation add 99.6mmol nonylcarbinol and 99.6mmol triethylamine successively, 55 ℃ were reacted 4 hours down.The product organic phase is used 1M HCl solution, saturated NH respectively
4Cl solution, and deionized water wash.Merge organic phase then, anhydrous magnesium sulfate drying filters, and concentrates the crude product that obtains and obtains 4-chlorosulfonyl phthalate ester decanoate through underpressure distillation.
(3) 4-sulfydryl phthalate ester decanoate is synthetic
Get step product 10.2mmol and place the 250ml round-bottomed flask, use the 5.0ml acetate dissolution, 4.6g SnCl
2Be dissolved among the 100ml HCl and process reductive agent, stir down dropwise dropping, add the back and keep 70 ℃, stopped reaction after 8 hours.With 250ml dichloromethane extraction water for several times, use 1mol/L NaHCO then successively
3, the de-ionized washing, organic phase is used anhydrous magnesium sulfate drying, filters, and underpressure distillation obtains crude product, again through column chromatography (elutriant: chloroform) separate, obtain 4-sulfydryl phthalate ester decanoate.
(1) 4-chlorosulfonyl phthalyl chloride is synthetic
This step is with embodiment 1 step (1).
(2) 4-chlorosulfonyl Witcizer 300 is synthetic
Get the product 33.2mmol in a step, place the 500ml round-bottomed flask, add 250ml trichloromethane stirring and dissolving, under agitation add 88mmol propyl carbinol and 88mmol triethylamine successively, 55 ℃ were reacted 4 hours down.The product organic phase is used 1M HCl solution, saturated NH respectively
4Cl solution, and deionized water wash.Merge organic phase then, anhydrous magnesium sulfate drying filters, and concentrates the crude product that obtains and obtains 4-chlorosulfonyl Witcizer 300 through underpressure distillation.
(3) 4-sulfydryl n-butyl phthalate is synthetic
Get step product 10.2mmol and place the 250ml round-bottomed flask, use the 5.0ml acetate dissolution, 4.6g SnCl
2Be dissolved among the 100ml HCl and process reductive agent, stir down dropwise dropping, add the back and keep 70 ℃, stopped reaction after 8 hours.With 250ml dichloromethane extraction water for several times, use 1mol/L NaHCO then successively
3, deionized water wash, organic phase is used anhydrous magnesium sulfate drying, filters, and underpressure distillation obtains crude product, again through column chromatography (elutriant: chloroform) separate, obtain 4-sulfydryl n-butyl phthalate.
Sulfydryl substituted benzene dicarboxylic acid esters is as the application of PVC softening agent
Among the present invention, softening agent is following to the modification procedure of PVC: the sulfydryl phthalic acid ester of weighing PVC (in structural unit) and equivalent is dissolved in it in pimelinketone or the pentanone 60 ℃ of constant temperature of heating in nitrogen atmosphere, stirring reaction.Reaction formula is as follows:
Be reacted to certain hour and reaction solution be poured in water and the mixing solutions of methyl alcohol with the 2:1 proportional arrangement termination reaction.As the washing and depositing system, cleaning is modified good PVC with THF/ normal hexane mixing solutions, solution is dried up promptly obtain with DOP plasticising and cross the faint yellow film of the similar flexible PVC of PVC.
Through nmr spectrum (
1H NMR) can the chemical structure of softening agent be characterized.With 4-sulfydryl o-benzoic acid di-n-octyl is example, and we analyze its nuclear magnetic spectrogram, and are as shown in Figure 1.
Be illustrated in figure 2 as PVC nmr spectrum through the modification of 4-sulfydryl dinoctyl phthalate.
The percentage of grafting of PVC (GR) can be with modified PVC
1The following formula of HMNR data substitution calculates.
For 4-sulfydryl phthalic ester,
I(aromatic) be meant peak value between the 7-8ppm; And for 5-sulfydryl isophthalic acid ester; Be meant the peak value between the 8-9ppm, the 3-5ppm position comprised all connect sulphur and chlorine-peak value of CH-and each modify four hydrogen on the ester group α carbon location in the group, latter's usefulness
The expression, need from
In deduct.
Fig. 3 is seen in the variation of modified PVC second-order transition temperature; As can be seen from the figure the second-order transition temperature of PVC reduces along with the increase of percentage of grafting gradually; When percentage of grafting reached 30% left and right sides, the second-order transition temperature of PVC reduced significantly, can satisfy under the normal temperature and use.
The percentage of grafting of softening agent can be regulated through the reaction times, and can calculate the percentage of grafting of softening agent on PVC through nmr spectrum.Environmental pollution and destruction that the present invention is to use this compounds can avoid the migration of small molecules softening agent (DOP) to cause with an important reasons of sulfydryl ester of phthalic acid class modified PVC, therefore the mobility test to this compounds is very necessary.Through contrived experiment, at room temperature extract the softening agent in the modified PVC with normal heptane, confirm its mobility according to the content of this compounds in the extraction liquid.Experiment shows: DOP grows with time and can constantly move in the blend, and grafted 4-sulfydryl dinoctyl phthalate then can not move out because there is chemical bond to link to each other with PVC.
As shown in Figure 4, just beginning in the for some time of soaking, the content of DOP increases sharply in the soak solution, is passing through the long time, and after about 3 ~ 4 hours, the migration of DOP has reached balance, and DOP content no longer increases in the solution.And concerning with the PVC of 4-sulfydryl dinoctyl phthalate chemical modification; Even after through more than 30 hours immersion, still do not have softening agent to overflow in the solution; Because sulfhydryl compound is grafted on the PVC, formed stable chemical bond, in general environment for use, can not change; It is stable for a long time that modified PVC can keep, and also can not damage environment.To expand the range of application of PVC undoubtedly greatly to this improvement of PVC.
Claims (6)
1. a plasticizer for polyvinyl chloride is characterized in that, structure is shown in logical formula I or (II):
The logical formula II of logical formula I
Wherein, R is the aliphatic group of straight or branched:
, n is 2～7 integer.
2. the preparation method of plasticizer for polyvinyl chloride according to claim 1 is characterized in that, concrete steps are following:
(1) dichloro-acetyl substituted benzene SULPHURYL CHLORIDE is synthetic
Sulfonic acid substituted benzene diformate and PCl
5Mix, 170～180 ℃ of heating added solvent after 15～20 hours, continue to stir, and cooling, underpressure distillation obtains dichloro-acetyl substituted benzene SULPHURYL CHLORIDE;
(2) chlorosulfonyl substituted benzene dicarboxylic acid esters is synthetic
Get a step product and mix with solvent, alcohols and organic amine, heated and stirred, Heating temperature are 55～70 ℃, and the reaction times is 1～4h; After reaction finished, reaction solution was used diluted acid respectively, saturated NH
4The Cl aqueous solution and water washing merge organic phase, and be dry, filter, concentrate and obtain chlorosulfonyl substituted benzene dicarboxylic acid esters, and wherein alcohols is the Fatty Alcohol(C12-C14 and C12-C18) of straight or branched, and structural formula is CH
3(CH
2) n CH
2OH, n are 2～7 integer, and said dichloro-acetyl substituted benzene SULPHURYL CHLORIDE is 1:3～1:2 with the mol ratio of alcohol, and the mol ratio of dichloro-acetyl substituted benzene SULPHURYL CHLORIDE and organic amine is 1:3～1:2;
(3) sulfydryl substituted benzene dicarboxylic acid esters is synthetic
Get the product that step 2 obtains and be dissolved in the acetate, add SnCl
2/ HCl reductant solution, heated and stirred, Heating temperature are 50～70 ℃, the reaction times is 8～15h; Reaction finishes, and uses organic solvent extraction, uses NaHCO then respectively
3Clean with water, organic phase is dry, filter, concentrate bullion, purify through column chromatography for separation again and obtain title product.
3. the preparation method of softening agent according to claim 2, it is characterized in that: the solvent in the step (1) is a kind of of benzene, toluene or YLENE.
4. the preparation method of softening agent according to claim 2 is characterized in that: sulfonic acid substituted benzene diformate and PCl described in the step (1)
5Mol ratio be 1:3～2:5.
5. the preparation method of softening agent according to claim 2, it is characterized in that: the solvent in the step (2) is chloroform or toluene.
6. the preparation method of softening agent according to claim 2, it is characterized in that: used organic amine is triethylamine or pyridine in the step (2).
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| CN111849556A (en) * | 2020-06-19 | 2020-10-30 | 安徽星鑫化工科技有限公司 | Modified chlorinated paraffin, and preparation method and application thereof |
| CN116080222A (en) * | 2022-12-30 | 2023-05-09 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
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| US20120149498A1 (en) * | 2008-01-10 | 2012-06-14 | Sullivan Michael J | Multi-layer core golf ball |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111849556A (en) * | 2020-06-19 | 2020-10-30 | 安徽星鑫化工科技有限公司 | Modified chlorinated paraffin, and preparation method and application thereof |
| CN116080222A (en) * | 2022-12-30 | 2023-05-09 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
| CN116080222B (en) * | 2022-12-30 | 2024-04-05 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
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Application publication date: 20121010 |