CN105153423A - Degradable polymer containing silicon ester bonds and application of degradable polymer - Google Patents
Degradable polymer containing silicon ester bonds and application of degradable polymer Download PDFInfo
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- CN105153423A CN105153423A CN201510679439.6A CN201510679439A CN105153423A CN 105153423 A CN105153423 A CN 105153423A CN 201510679439 A CN201510679439 A CN 201510679439A CN 105153423 A CN105153423 A CN 105153423A
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Abstract
The invention discloses a degradable polymer containing silicon ester bonds. The degradable polymer is poly[2,2-bis(p-dimethyl siloxyphenyl)propane sebacate]. The invention further discloses an application of the degradable polymer as a drug carrier in pharmacy. Experiments prove that the release velocity of the degradable polymer as the drug carrier to tested drugs is basically synchronous with the degradation of the degradable polymer, and the degradable polymer is expected to be widely applied in the fields such as pharmacy, preparation of adhesives and the like.
Description
Technical field
The present invention relates to a kind of degradable polymer and application thereof, particularly relate to a kind of degradable polymer and the application thereof that contain estersil key, belong to polymeric material field.
Background technology
Degradable polymer refers to the material that to be formed after completing use task and absorbed by environmental and biological materials or becomes the material harmless to environmental and biological materials.Because it has eco-friendly " green material ", cause the extensive concern of people in recent years and become study hotspot.
In degradable polymer main chain containing estersil key, silica-based ester structure is easy to the attack being subject to nucleophilic reagent or electrophilic reagent, its degraded scope is expanded greatly, very easily be degraded into small molecules, therefore its exploitation and Selection utilization are expected to research and development application in biomedicine and pharmaceutical carrier, adhesive agent etc. provides basis and foundation, has good development prospect.
In the document of the existing degradable polymer containing estersil key of retrieval, document or the patent of relevant poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-] have not been reported.
Summary of the invention
For the situation of current technology, the invention provides a kind of degradable polymer and the application thereof that contain estersil key.
Degradable polymer containing estersil key of the present invention is poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-], and its chemical structural formula is:
Poly[2,2-bis(p-dimethylsiloxy-phenyl)propanesebacate]
The weight-average molecular weight of above-mentioned poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-] is 9842.
The preparation method of above-mentioned poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-], step is:
1) two (p-dimethyl-chlorine siloxy benzene) oxide monomer of 2,2-is prepared:
Under nitrogen atmosphere protection, ratio, by dihydroxyphenyl propane: dimethyldichlorosilane(DMCS): tetrahydrofuran (THF) is that 1:2.0:4.0 ~ 6.0 are reacted in there-necked flask; after reaction terminates; except desolventizing, obtain two (p-dimethyl-chlorine siloxy benzene) propane of monomer 2,2-.
2) sebacic acid di-t-butyl ester monomer is prepared:
Under protection of inert gas, ratio, takes sebacic acid: sulfur oxychloride is 1:4.0-6.0, and adds the mixed solution that volume ratio is the benzene/cyclohexane of 2:1, low-grade fever 2.5h, then air distillation, removing hexanaphthene and remaining thionyl chloride.With ether, sebacic acid diacid chloride is transferred to constant voltage to drip in funnel at night.Be add in there-necked flask after the DMA of 1:1 and the trimethyl carbinol mix with anhydrous diethyl ether by mol ratio, stir.Drip sebacic acid diacid chloride, after dropwising rear normal-temperature reaction 20h, reaction mixture dilutes through NaCl solution, then extracts with anhydrous diethyl ether.Organic layer washs three times with the mixed solution of 2mol/L salt solution and saturated aqueous common salt more successively, and the NaOH solution of 1mol/L and the mixed solution of saturated aqueous common salt wash three times, then use saturated common salt water washing once.Organic layer first carries out air distillation, then carries out underpressure distillation, obtains sebacic acid di-t-butyl ester monomer.
3) preparation poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-]:
Under protection of inert gas, ratio, by two for 2,2-(p-dimethyl-chlorine siloxy benzene) propane: sebacic acid di-t-butyl ester is that 1:1 mixes, through vacuumizing, logical rare gas element carries out polycondensation in the there-necked flask of three times repeatedly.Polymeric reaction temperature is 80-130 DEG C, and the reaction times is 60-120h, is namely gathered [two (p-dimethyl silica phenyl) the propane sebate of 2,2-].
In the preparation method of above-mentioned poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-]: step 1) feed postition of described dimethyldichlorosilane(DMCS) adopts constant pressure funnel to drip in there-necked flask; Described Heating temperature is for keeping micro-backflow; The described reaction times is 4h.
Above-mentioned poly-[2, two (p-dimethyl silica phenyl) the propane sebate of 2-] preparation method in: step 2) volume ratio of described 2mol/L salt solution and saturated common salt water mixed liquid be the NaOH solution of 3:1,1mol/L and the volume ratio of saturated aqueous common salt is also 3:1; Step 2) time for adding of described sebacic acid diacid chloride is 5 ~ 10min.
In the preparation method of above-mentioned poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-]: step 3) described polymeric reaction temperature is 100-110 DEG C, the reaction times is 80 ~ 100h.
In the preparation method of above-mentioned poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-]: step 3) described there-necked flask must be clean dried; Described rare gas element is the nitrogen of purity by quality ratio more than 99.99%.
In the preparation method of above-mentioned poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-]: step 3) described in vacuumize be adopt oil pump to vacuumize, vacuum tightness is 0.08 ~ 0.1MPa.
Above-mentioned poly-[2,2-two (p-dimethyl silica phenyl) propane last of the ten Heavenly stems], the preparation feedback formula of two acid esters was as follows:
Degradable polymer containing estersil key of the present invention is as the application of pharmaceutical carrier in pharmacy.
Wherein, described polymer poly [2,2-two (p-dimethyl silica phenyl) propane last of the ten Heavenly stems] to be preferably weight-average molecular weight be 9842 for the molecular weight of two acid esters, utilizes its result of carrying out medicament slow release experiment as pharmaceutical carrier to show: polymkeric substance is basic synchronous with its degraded to the rate of release of testing drug PNA.Indicate that it is expected to be widely used at pharmacy field as pharmaceutical carrier.
The invention discloses a kind of degradable polymer containing estersil key poly-[2,2-two (p-dimethyl silica phenyl) propane last of the ten Heavenly stems] two acid esters, this polymkeric substance carries out polycondensation with di-carboxylic acid di-t-butyl ester and chlorosilane to synthesize and obtain.Preparation method of the present invention is compared with the chemical synthesis process of the existing polymkeric substance containing silica-based ester, and beneficial effect is:
1. adopt polycondensation to obtain, reaction conditions is gentle, simple to operate, releases lower boiling tertiary butyl chloride by product, is conducive to the carrying out of polycondensation.
2., compared to silicon transfer ester interchange polymerization method, the reaction times reduces relatively; Compared to hydrosilation polymerization and dehydrogenation linked reaction of intersecting, relatively much lower to the requirement of the series reaction such as reaction monomers, solvent thing.
The invention also discloses the described degradable polymer containing estersil key as the application of pharmaceutical carrier in pharmacy, it is basic synchronous with its degraded to the rate of release of testing drug as pharmaceutical carrier that experiment confirms to utilize it.Indicate that it is expected to the field such as to prepare at pharmacy, adhesive agent and is widely used.
Accompanying drawing explanation
The relative molecular weight of Fig. 1 poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-] and distribution curve thereof.
Embodiment
For being easy to understand the present invention further, below in conjunction with embodiment, the present invention is further elaborated.
The preparation of embodiment 1 poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-] of the present invention
1) under the protection of nitrogen (purity is by quality ratio more than 99.99%) atmosphere; number meter in molar ratio; 1 part of dihydroxyphenyl propane is added in there-necked flask, in there-necked flask, drips 2 parts of dimethyldichlorosilane(DMCS)s with constant pressure funnel, then 5 parts of tetrahydrofuran (THF)s are added.After reinforced, heating keeps micro-backflow, reaction 4h, and after reaction terminates, removal of solvent under reduced pressure, obtains two (p-dimethyl-chlorine siloxy benzene) the propane organosilicon chlorine monomer of 2,2-.
2) under the protection of nitrogen (purity is by quality ratio more than 99.99%) atmosphere, number meter in molar ratio, by 1 part of sebacic acid, 4 parts of sulfur oxychlorides, add volume ratio be 2:1 the mixed solution of benzene/cyclohexane, low-grade fever 2.5h, then air distillation.With ether, sebacic acid diacid chloride is transferred to constant voltage to drip in funnel at night.Add in there-necked flask after 1 part of DMA and 1 part of trimethyl carbinol mix with 3 parts of anhydrous diethyl ethers, stir.Drip sebacic acid diacid chloride, after dropwising, after normal-temperature reaction 20h, reaction mixture dilutes through NaCl solution, then extracts with anhydrous diethyl ether.Organic layer washs three times with the mixed solution of 2mol/L salt solution and saturated aqueous common salt more successively, and the NaOH solution of 1mol/L and the mixed solution of saturated aqueous common salt wash three times, then use saturated common salt water washing once.Wherein, the volume ratio of described 2mol/L salt solution and saturated common salt water mixed liquid is 3:1, and the NaOH solution of described 1mol/L and the volume ratio of saturated aqueous common salt are also 3:1.
Organic layer first carries out air distillation, then carries out underpressure distillation, obtains sebacic acid di-t-butyl ester monomer.
3) under the protection of nitrogen (purity is by quality ratio more than 99.99%) atmosphere (reaction system process vacuumizes, leads to nitrogen three times repeatedly); number meter in molar ratio; by 1 part 2; two (p-dimethyl-chlorine siloxy benzene) propane of 2-, 1 part of sebacic acid di-t-butyl ester are that monomer reacts at 100 DEG C; reaction times is 60h; obtain target product poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-].
Molecular weight determination: the weight-average molecular weight of polymer poly [2,2-two (p-dimethyl silica phenyl) propane last of the ten Heavenly stems] two acid esters is 9842, and its relative molecular weight and distribution curve thereof are shown in Fig. 1.
Poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-] that embodiment 2 utilizes embodiment 1 to prepare carries out medicament slow release experiment
P-Nitroaniline and poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-] are mixed, mass ratio is 10%.Grind in mortar, being molded into print diameter with infrared tabletting machine is 13mm, thickness 0.8 ~ 1mm (90MPa, room temperature, 5min).Be placed in the phosphate buffer soln of the 0.1mol/LpH=7.4 of 10mL respectively, carry out drug release experiment in 37 ± 0.5 DEG C of constant temperature static state.
Get release liquid at regular intervals appropriate, add equal-volume blank medium simultaneously, adopt the absorbancy of ultraviolet spectroscopy release medium at wavelength 380nm place.Calculate the drug level that is released in buffered soln and calculate cumulative release percentage.
Experimental result shows: polymkeric substance is basic synchronous with its degraded to the rate of release of PNA.Indicate that it is expected to the field such as to prepare at pharmacy, adhesive agent and is widely used.
Claims (3)
1. the degradable polymer containing estersil key, is characterized in that: described polymkeric substance is poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-], and its chemical structural formula is:
2. the degradable polymer containing estersil key as claimed in claim 1, is characterized in that: the weight-average molecular weight of described poly-[two (p-dimethyl silica phenyl) the propane sebate of 2,2-] is 9842.
3. the degradable polymer containing estersil key described in claim 1 or 2 is as the application of pharmaceutical carrier in pharmacy.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225358A (en) * | 2005-02-21 | 2006-08-31 | Shiseido Co Ltd | Siloxane ester compound, oil component for skin care preparation or hair cosmetic, and skin care preparation or hair cosmetic prepared by compounding the oil component |
| US20080145405A1 (en) * | 2006-12-15 | 2008-06-19 | Kunzler Jay F | Drug delivery devices |
| CN104119520A (en) * | 2014-05-12 | 2014-10-29 | 杭州师范大学 | Biodegradable material containing ladder-like polysilsesquioxane and preparation method of biodegradable material |
-
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- 2015-10-19 CN CN201510679439.6A patent/CN105153423A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225358A (en) * | 2005-02-21 | 2006-08-31 | Shiseido Co Ltd | Siloxane ester compound, oil component for skin care preparation or hair cosmetic, and skin care preparation or hair cosmetic prepared by compounding the oil component |
| US20080145405A1 (en) * | 2006-12-15 | 2008-06-19 | Kunzler Jay F | Drug delivery devices |
| CN104119520A (en) * | 2014-05-12 | 2014-10-29 | 杭州师范大学 | Biodegradable material containing ladder-like polysilsesquioxane and preparation method of biodegradable material |
Non-Patent Citations (3)
| Title |
|---|
| NIANFENG HAN，等: "Preparation and Characterization of Poly(silyl ester)sContaining 2,2-Bis(p-dimethylsiloxy-phenyl)propane Units in the Polymer Backbones", 《APPLIED POLYMER》 * |
| 岳芸，等: "新型可降解聚硅基酯的合成及性质研究", 《化工新型材料》 * |
| 韩念凤，等: "用二元羧酸二叔丁基酯与氯硅烷缩聚合成新聚硅基酯研究", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技I辑》 * |
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