CN107163237A - The method that hydrogen chloride/diethyl ether solution catalysis prepares PCL PDMS PCL stabilizers - Google Patents

The method that hydrogen chloride/diethyl ether solution catalysis prepares PCL PDMS PCL stabilizers Download PDF

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Publication number
CN107163237A
CN107163237A CN201710388747.2A CN201710388747A CN107163237A CN 107163237 A CN107163237 A CN 107163237A CN 201710388747 A CN201710388747 A CN 201710388747A CN 107163237 A CN107163237 A CN 107163237A
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pcl
pdms
hydrogen chloride
diethyl ether
ether solution
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詹世平
邓进军
王景昌
侯维敏
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Dalian University
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Dalian University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to the method that a kind of hydrogen chloride/diethyl ether solution catalysis prepares PCL PDMS PCL stabilizers.Hydroxypropyl terminated dimethyl silicone polymer (HTPDMS) is used for initiator, with hydrogen chloride/diethyl ether solution (HClEt2O) it is catalyst, triggers ε caprolactones (ε CL) ring-opening polymerisation, be prepared for three block stabilizer polycaprolactone b dimethyl silicone polymer b polycaprolactones (PCL PDMS PCL).By infrared spectrum and proton nmr spectra analysis shows, the molecule of synthesis is consistent with target molecular structure.It is preferred that reaction condition be 25 DEG C of reaction temperature, reaction time 4h, HClEt2O and HTPDMS mol ratio is 2:1.The present invention uses hydrogen chloride/diethyl ether solution for catalyst, overcome the problem of metallic catalyst generally used is brought, prepare environment more green, the reaction time substantially shortens, the three block stabilizer of preparation can be used for the dispersant that biological medicine material polymerize in supercritical fluid.

Description

The method that hydrogen chloride/diethyl ether solution catalysis prepares PCL-PDMS-PCL stabilizers
Technical field
The present invention relates to technical field of macromolecule polymerization, specifically hydrogen chloride/diethyl ether solution catalysis prepares PCL-PDMS- The method of PCL stabilizers.
Background technology
Supercritical carbon dioxide (ScCO2) technology turn into numerous scholar's research heat subject, due to its have source Extensively, there are the diffusivity of similar gas and the density of liquid, nontoxic, inertia, the easily separated purifying of reaction product, make it For a kind of green solvent instead of many poisonous and hazardous organic solvents and is widely studied and applied, especially scattered poly- Conjunction field is also able to promote and use.
Supercritical carbon dioxide can dissolve the nonpolar molecule and some polar molecules of most of low molecule amounts, but most of Industrial widely used polymer can not be but dissolved under the conditions of relatively mild, only unformed fluoropolymer and silicon Oxygen alkane polymer can be completely dissolved in supercritical carbon dioxide, therefore, and most of polymerisations in supercritical carbon dioxide are It is heterogeneous, i.e. precipitation polymerization.There are some shortcomings in precipitation polymerization, such as conversion ratio is low, and molecular weight of product is smaller and product shape State is irregular etc.., can be in polymer in the presence of stabilizer and dispersin polymerization can be largely overcoming these shortcomings Certain active force with the formation of solvent interface, produces steric effect to prevent the solidifying of particle by physical absorption or chemical graft Poly-, dispersin polymerization can improve reaction efficiency and yield.The effect of dispersin polymerization is largely dependent on the effect of dispersion stabilizer Effect.Prepare at present dispersion stabilizer more and use metallic catalyst, it is longer using the preparation method reaction time of metallic catalyst, Generally require 24~48h, and toxic side effect, therefore the good stabilizer of exploitation environmental protection, with low cost and anchoring effect It is very important.
The content of the invention
It is an object of the invention to provide a kind of side that PCL-PDMS-PCL stabilizers are prepared with ether solution of hydrogen chloride catalysis Method.
For achieving the above object, technical scheme is as follows：
The method that hydrogen chloride/diethyl ether solution catalysis prepares PCL-PDMS-PCL stabilizers, with hydroxypropyl terminated poly- diformazan Radical siloxane (HTPDMS) is initiator, with hydrogen chloride/diethyl ether solution (HClEt2O it is) catalyst, initiation 6-caprolactone (ε- CL) ring-opening polymerisation, prepares three block stabilizer polycaprolactone-b- dimethyl silicone polymer-b- polycaprolactones (PCL-PDMS- PCL), synthetic route is as follows：
The above method comprises the following steps：
(1) HTPDMS, dichloromethane, ε-CL are added in flask, then add HClEt2O solution, 15~35 Stirred 3~5 hours at DEG C, and argon gas is protected；Wherein HClEt2O and HTPDMS mol ratio is 2~6:1, HTPDMS and ε- CL monomer weight ratios are 1:1~2；
(2) after the reaction of step (1) terminates, add after 300mL cold methanols, Precipitation product and filter, then be dried in vacuo, PCL-PDMS-PCL stabilizers are obtained, reaction scheme is as follows：
Preferably due to which the two ends of HTPDMS chains are respectively containing a hydroxyl for playing initiation, according to triggering mechanism Select HClEt2O and HTPDMS mol ratio is 2:1.
Preferably, reaction temperature is 25 DEG C in step (1), stirs 4h.
Synthesis mechanism：The cation of hydrogen chloride/diethyl ether solution catalyst generates positive oxygen ion, caprolactone with 6-caprolactone Carbonyl be activated, then, the hydroxyl radical attacks active carbonyl group at dimethyl silicone polymer two ends promotes caprolactone ring-opening polymerisation, acyl Oxygen bond rupture, reaction principle route is shown in Fig. 1.
Compared with prior art, the advantage of the invention is that：The present invention uses hydrogen chloride/diethyl ether solution for catalyst, instead Answer condition gentleer, it is to avoid using the toxic side effect of metallic catalyst, prepare that environment is more green, the reaction time substantially contracts It is short, its molecular weight of the three block stabilizer PCL-PDMS-PCL of preparation up to 6384g/mol, yield can reach 86% with On, the stabilizer can be used for the dispersant that biological medicine material polymerize in supercritical fluid, available in supercritical carbon dioxide The synthesis of the aliphatic polyesters such as biomaterial PLA, polycaprolactone and its copolymer and the synthesis of other functional materials.
Brief description of the drawings
Fig. 1 composition principle figures of the present invention；
Fig. 2 PCL-PDMS-PCL infrared spectrograms；
Fig. 3 PCL-PDMS-PCL proton nmr spectra spectrograms.
Embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
By load weighted HTPDMS 5g (0.0015mol), dichloromethane 30mL, the ε-CL 5g of water removal are dried (0.044mol) is added in 50mL three neck round bottom flask, then adds 4.2mol/L HClEt2O solution 0.71mL (0.003mol), is stirred 4 hours at 25 DEG C, and argon gas is protected；After reaction terminates, add in 300mL cold methanols, Precipitation production Filtered after thing, vacuum dried to obtain product PCL-PDMS-PCL8.6g, molecular weight is 6384g/mol, and yield is 86%.
Embodiment 2
By load weighted HTPDMS 5g (0.0015mol), dichloromethane 30mL, the ε-CL 5g of water removal are dried (0.044mol) is added in 50mL three neck round bottom flask, then adds 4.2mol/L HClEt2O solution 1.42mL (0.006mol), is stirred 4 hours at 25 DEG C, and argon gas is protected；After reaction terminates, add in 300mL cold methanols, Precipitation production Filtered after thing, vacuum dried to obtain product PCL-PDMS-PCL8.5g, molecular weight is 6016g/mol, and yield is 85%.
Embodiment 3
By load weighted HTPDMS 5g (0.0015mol), dichloromethane 30mL, the ε-CL 5g of water removal are dried (0.044mol) is added in 50mL three neck round bottom flask, then adds 4.2mol/L HClEt2O solution 0.71mL (0.003mol), is stirred 4 hours at 35 DEG C, and argon gas is protected；After reaction terminates, add in 300mL cold methanols, Precipitation production Filtered after thing, vacuum dried to obtain product PCL-PDMS-PCL7.8g, molecular weight is 6023g/mol, and yield is 78%.
Fig. 2 is the three block stabilizer PCL-PDMS-PCL obtained in embodiment 1 infrared spectrogram.In 3543cm-1Place For the stretching vibration peak of product terminal hydroxy group (- OH), in 2961cm-1And 2865cm-1Locate as the methylene of PCL in PCL-PDMS-PCL The C-H stretching vibration peaks of base, in 1735cm-1Locate as carbonyl in PCL (C=O) stretching vibration peak, in 800cm-1Locate as PDMS The stretching vibration peak of middle Si-C keys, in 1092cm-1Locate as the stretching vibration peak of Si-O keys in PDMS main chains.The above results show, Absworption peak in spectrogram meets PCL-PDMS-PCL characteristic absorption peak.
Fig. 3 is the three block stabilizer PCL-PDMS-PCL obtained in embodiment 11H-NMR spectrum.1HNMR(CDCl3, ppm)：4.04–4.07[t,COOCH 2CH2,Ha+e]；2.28–2.32[t,CH2 CH 2COO,Hd]；1.60–1.68[m, COOCH2 CH 2CH2and CH2 CH 2CH2COO,Hb+f]；1.35–1.41[m,OOCH2CH2CH2,Hc]；0.48–0.55[t, CH2CH2 CH 2Si,Hg]；0.03–0.09[m,Si(CH 3)2,Hh].Wherein, the peak at 0.05ppm and 0.5ppm is poly dimethyl silicon The characteristic peak of oxygen alkane, 1.7ppm and 2.3ppm are the characteristic signal of caprolactone repeat unit, it was demonstrated that polymer is that three block is steady Determine agent PCL-PDMS-PCL.
By infrared spectrum Fig. 2 and nuclear magnetic resonance Fig. 3 analysis shows, the three block catalyzed and synthesized through hydrogen chloride/diethyl ether solution Stabilizer PCL-PDMS-PCL structure is consistent with the target molecular structure designed.
With hydrogen chloride/diethyl ether solution as catalyst, the work of activator is only served during PCL-PDMS-PCL is prepared With being not belonging to initiator；This method reaction time substantially shortens, than stannous octoate catalytic reaction time fast 20h；Prepare environment more Plus green, it is a kind of synthetic method of the stabilizer with development potentiality, meets the direction of green chemistry, there is wide Application prospect.

Claims (4)

1. the method that hydrogen chloride/diethyl ether solution catalysis prepares PCL-PDMS-PCL stabilizers, it is characterised in that methods described is with hydroxyl The dimethyl silicone polymer (HTPDMS) of propyl group end-blocking is initiator, with hydrogen chloride/ether (HClEt2O) solution is catalysis Agent, triggers 6-caprolactone (ε-CL) ring-opening polymerisation, prepares polycaprolactone-b- dimethyl silicone polymer-b- polycaprolactones (PCL- PDMS-PCL), synthetic route is as follows：
2. the method that hydrogen chloride according to claim 1/diethyl ether solution catalysis prepares PCL-PDMS-PCL stabilizers, it is special Levy and be, the described method comprises the following steps：
(1) HTPDMS, dichloromethane, ε-CL are added in flask, then add HClEt2O solution, is stirred at 15~35 DEG C Mix 3~5 hours, and argon gas is protected；Wherein HClEt2O and HTPDMS mol ratio is 2~6:1, HTPDMS with ε-CL monomers Mass ratio is 1:1~2；
(2) after the reaction of step (1) terminates, add after 300mL cold methanols, Precipitation product and filter, then be dried in vacuo, produce To PCL-PDMS-PCL stabilizers.
3. the method that hydrogen chloride according to claim 1/diethyl ether solution catalysis prepares PCL-PDMS-PCL stabilizers, it is special Levy and be, HClEt2O and HTPDMS mol ratio is 2:1.
4. the method that hydrogen chloride according to claim 1/diethyl ether solution catalysis prepares PCL-PDMS-PCL stabilizers, it is special Levy and be, reaction temperature is 25 DEG C in step (1), stirs 4h.
CN201710388747.2A 2017-05-27 2017-05-27 The method that hydrogen chloride/diethyl ether solution catalysis prepares PCL PDMS PCL stabilizers Pending CN107163237A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN108948331A (en) * 2018-06-11 2018-12-07 大连大学 A kind of method of boric acid catalysis open loop dispersin polymerization caprolactone in supercritical carbon dioxide
CN109776970A (en) * 2018-12-27 2019-05-21 会通新材料股份有限公司 A kind of PP composite material for automobile interiors and preparation method thereof
CN111961207A (en) * 2020-07-08 2020-11-20 大连大学 Method for synthesizing caprolactone and dimethyl siloxane triblock copolymer by using citric acid as catalyst

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108948331A (en) * 2018-06-11 2018-12-07 大连大学 A kind of method of boric acid catalysis open loop dispersin polymerization caprolactone in supercritical carbon dioxide
CN109776970A (en) * 2018-12-27 2019-05-21 会通新材料股份有限公司 A kind of PP composite material for automobile interiors and preparation method thereof
CN111961207A (en) * 2020-07-08 2020-11-20 大连大学 Method for synthesizing caprolactone and dimethyl siloxane triblock copolymer by using citric acid as catalyst
CN111961207B (en) * 2020-07-08 2022-08-02 大连大学 Method for synthesizing caprolactone and dimethyl siloxane triblock copolymer by using citric acid as catalyst

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