CN110066355A - Degradable poly styrene and preparation method thereof - Google Patents
Degradable poly styrene and preparation method thereof Download PDFInfo
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- CN110066355A CN110066355A CN201910357773.8A CN201910357773A CN110066355A CN 110066355 A CN110066355 A CN 110066355A CN 201910357773 A CN201910357773 A CN 201910357773A CN 110066355 A CN110066355 A CN 110066355A
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 65
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 125000004185 ester group Chemical group 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- -1 o-nitrobenzyl ester Chemical class 0.000 claims description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002228 disulfide group Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002861 polymer material Substances 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000002144 chemical decomposition reaction Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007342 radical addition reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 238000007068 beta-elimination reaction Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 208000034158 bleeding Diseases 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- FIAPRFVULRVTAN-UHFFFAOYSA-N carbon monoxide;styrene Chemical compound O=[C].C=CC1=CC=CC=C1 FIAPRFVULRVTAN-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 125000006285 dibromobenzyl group Chemical group 0.000 description 1
- BQFFOAXUGJJYNZ-UHFFFAOYSA-N dichloromethane;sulfuric acid Chemical compound ClCCl.OS(O)(=O)=O BQFFOAXUGJJYNZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses the degradable poly styrene and preparation method thereof with structure shown in general formula I, include the following steps: (1) by dihalo object, dicarboxyl acid initiator and organic base are added into solvent, obtain macromole evocating agent solution after reacting at room temperature；(2) under an inert atmosphere, macromole evocating agent solution obtained in step (1) is blended at 75 DEG C with styrene monomer and is reacted, obtain the more block polystyrene solution of ester group；(3) solution in step (2) is added dropwise in poor solvent, is filtered, washing obtains subject polymer after dry.
Description
Technical Field
The invention relates to polystyrene and a preparation method thereof, in particular to degradable polystyrene and a preparation method thereof.
Background
Polystyrene and its copolymer are used as a general polymer material, the yield and consumption of which are second to those of polyethylene, polyvinyl chloride and polypropylene, and the polystyrene and its copolymer are widely applied to products such as electronic appliances, fast food boxes, packaging materials, building boards and the like. Since polystyrene is difficult to degrade under natural conditions, its waste can cause serious environmental pollution (panzuren, high molecular chemistry, 2007).
There are two main types of degradable polymer materials, namely blend type and synthetic type.
The blend type polymer material mainly comprises two types. One is prepared by blending synthetic polymer material such as polystyrene with natural polymer such as starch, cellulose, chitosan, etc. (Wuhan university bulletin 2000, 46, 449). Although natural polymers are degraded under natural conditions, polystyrene is not degraded or remains in natural environments. Therefore, it is still difficult to achieve complete degradation of such polymer materials (starch-based biodegradable materials, published by light industries of china, 2008). Another is to blend synthetic Polymer with photosensitizer, and induce the Polymer backbone to break and degrade by photochemical reaction (Photochemistry and Photophysics of Polymer Materials, 2010). However, these additives run the risk of bleeding during use and cause pollution to the surrounding environment, which limits their range of use.
The synthetic degradable high molecular material is made by introducing degradable groups into the main chain or side chain of olefin polymer, so that the polymer has degradability. Introduction of carbonyl, ester and other degradable groups into the polystyrene main chain is a basic strategy for preparing degradable polystyrene. According to literature research, there are several methods for introducing degradable functional groups into polystyrene main chains:
(1) alternating copolymerization of styrene and carbon monoxide (chem.res., 1993, 26, 303). Although the styrene-carbon oxide alternating copolymer obtained by the method has light degradation performance, the high content of carbonyl greatly influences the mechanical property and the thermal property of the material.
(2) Free radical random copolymerization of styrene with unsaturated cyclic acetal monomers (J.Polym.Sci., Part A: Polym.Chem., 1993, 31, 3159) (J.environ.Polym.Degrad., 1998, 6, 23). Unsaturated cyclic acetal monomers form ester groups in the polystyrene main chain after undergoing a free radical addition ring-opening reaction, but due to random copolymerization, the position of the ester groups in the main chain cannot be precisely controlled. In addition, the unsaturated cyclic acetal monomer has complex synthetic steps and is not easy to prepare.
(3) Atom transfer polymerization (ATRP) is combined with radical coupling reaction (Macromolecules, 2007, 40, 9217). first, polystyrene with bromine at both ends is synthesized by ATRP method, then radical coupling reaction is carried out with dinitrogen free radical containing degradable groups (such as ester group, disulfide bond and the like) under the catalysis of CuX/L and Cu (0), so as to obtain styrene polymer containing degradable groups in the main chain, but various side reactions (such as β -elimination and the like) can be carried out at the bromine end (Macromolecules. chem. phys., 2008, 209, 32.), so that the block number of the obtained target product is not high (DB < 10). furthermore, the obtained polymer is not stable to heat.
(4) Atom transfer polymerization is combined with a free radical addition coupling reaction (j.polym.sci.part a: polym.chem., 2011, 49, 612). Firstly, synthesizing polystyrene with bromine at two ends by using an ATRP bifunctional initiator containing an ester group, and then adding a nitroso compound under the catalysis of Cu (0)/L to generate a free radical addition coupling reaction (macro. Rapid Commun., 2011, 32, 1180.) to obtain a polymer with a main chain containing the ester group and a nitrogen-oxygen group. However, the thermal stability of the nitroxide group is poor, and the thermal properties of the polymer material are affected.
(5) Atom transfer polymerization is combined with click reactions (Macromolecules, 2005, 38, 3558). Firstly, synthesizing polystyrene containing ester groups and end groups of alkynyl and bromine in a main chain by using an ATRP method, then converting the tail end of the bromine into azido, and finally obtaining the polystyrene containing ester groups through click reaction. However, this method requires end group conversion of the polymer, and is liable to cause side reactions, resulting in a low number of blocks (DB < 10) for obtaining the target polymer.
As mentioned above, the prior art methods for introducing degradable groups into polymers all have their own disadvantages and limitations.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide degradable polystyrene.
The invention also aims to provide a preparation method of the degradable polystyrene.
The technical scheme is as follows: a degradable polystyrene having a structure represented by formula I:
wherein,
R1represents:
R2represents:
R3represents:
m and n represent: the number of the structural units in the degradable polystyrene chain segment is repeated.
Furthermore, the structure of the degradable polystyrene contains one or more of ester group, o-nitrobenzyl ester or disulfide group.
The preparation method of the degradable polystyrene is characterized by comprising the following steps: the method comprises the following steps:
wherein, X represents: -Br, -cl or-l,
(1) adding a dihalogen compound, a dicarboxylic acid initiator and an organic base into a solvent, and reacting at room temperature to obtain a macromolecular initiator solution;
(2) mixing the macromolecular initiator solution obtained in the step (1) with a styrene monomer under an inert atmosphere to react at 75 ℃ to obtain an ester-based multi-block polystyrene solution;
(3) and (3) dropwise adding the solution obtained in the step (2) into a poor solvent, filtering, washing and drying to obtain the target polymer.
Further, in the step (1), the dicarboxylic acid initiator is firstly mixed with the organic base in an ice-water bath. The organic base in the step (1) is one or more of tetramethylguanidine, 1, 8-diazabicycloundec-7-ene (DBU), sodium ethoxide, sodium methoxide, potassium tert-butoxide and alkyl metal lithium. The mass ratio of the macroinitiator solution to the styrene monomer in the step (2) is 1: 100-1: 500. The drying temperature in the step (3) is 35-90 ℃.
The polyester has good mechanical property, can be subjected to chemical degradation and biological degradation, and ester groups or polyester chain segments are efficiently and regularly embedded into a polystyrene main chain, so that the polystyrene high polymer material with degradability can be obtained.
The esterification reaction of carboxylic acid and halide promoted by tetramethylguanidine, 1, 8-diazabicycloundecen-7-ene (DBU), sodium ethoxide, sodium methoxide, potassium tert-butoxide, lithium alkyl and the like is not only suitable for the synthesis of small molecular carboxylic ester, but also suitable for the synthesis of polymethacrylate and polyacrylate acid, and the esterification degree is close to 100% (Polym.chem., 2013, 4, 2891). The method has the outstanding advantage that the esterification reaction can be completed quickly and efficiently at room temperature.
The basic idea is to combine the (active) free radical polymerization with the efficient esterification reaction promoted by tetramethylguanidine, and introduce the degradable groups such as ester groups into the main chain of polystyrene efficiently and regularly to obtain the degradable polystyrene.
Has the advantages that: the method has strong designability and controllability, and can regulate and control the length of the polystyrene chain segment, the quantity of degradable groups and the distribution of the degradable groups in a polymer chain. The polystyrene has the characteristics of small carbonyl content, high mechanical property and thermal property and good melt fluidity, and can accurately control the position of an ester group in a main chain. The main raw materials are industrial products, which is beneficial to realizing the industrial application of the degradable styrene polymer.
Drawings
FIG. 1 shows NMR spectra of P-dibromobenzyl, C1, P11H, spectrogram;
FIG. 2 is a DSC melting curve of P1, P7, PS.
Detailed Description
The hydrogen spectrum of nuclear magnetic resonance is measured by taking tetramethylsilane as an internal standard and deuterated chloroform as a solvent, measuring the molecular weight by a viscosity method and taking an Ubbelohde viscometer as an instrument, and taking tetrahydrofuran as a solvent under the condition of 25 ℃ and utilizing a formula [ η ]]Calculation is performed at kM ηα, where k is 12.58 × 10-3α -0.7155 melting index determination conditions, load is 5kg, temperature is 190 ℃, sampling interval is 20 s.DSC melting curve is determined by (NETZSCH corporation-DSC-200-F3), heating rate is 10 ℃/min, test temperature is 50-150 ℃, degradation mode is chemical degradation, degradation condition is that 10% sodium hydroxide water solution and 4% degradable polystyrene N, N-dimethyl formamide solution are mixed according to volume ratio of 1: 5, reaction is carried out at 75-90 ℃, degradation rate is calculated by taking degradation specific time product, washing, determining viscosity average molecular weight after drying, using formulaCalculation of where M0To viscosity average molecular weight before degradation, MiThe degradation is the viscosity average molecular weight after different time, and X is the degradation rate. PolystyreneThe preparation method of the standard sample (hereinafter referred to as PS) comprises the following steps: the initiator is Azobisisobutyronitrile (AIBN), the molar ratio of the initiator to the monomer is 1: 300, and the initiator is obtained by reaction under the same external conditions.
Example 1: preparation of P1
The preparation route is as follows:
wherein m and n represent: the number of the repeated structural units in the polystyrene chain segment, wherein n is determined by the ratio of the initiator to the monomer; m is determined by the ratio of azobiscyanovaleric acid to p-dibromobenzyl.
The preparation method comprises the following specific steps:
(1) synthesis of p-dibromobenzyl: sodium bromide (4.115g, 0.04mol), sodium bromate (3.018g, 0.02mol) was added to 70ml of water; p-xylene (3.185g, 0.03mol) was added to 70ml of dichloromethane; sulfuric acid (2.94g, 0.03mol) was added to 40ml of water. Mixing the first two solutions, dripping dilute sulfuric acid solution into the mixed solution, controlling the dripping speed to be about 3 seconds, and reacting for about 6 hours at room temperature. And after the reaction is finished, washing the product for 3 times, separating liquid, drying, rotationally evaporating the solvent, and recrystallizing to obtain the p-dibromide benzyl. The yield was 87%;
(2) azobiscyanovaleric acid (0.5g, 0.0018mol) and N, N-dimethylformamide (10mL) solvent were added to a round bottom flask. Tetramethylguanidine (0.411g, 0.0036mol) was added dropwise to the above solution under ice-water bath conditions. After completion of the dropwise addition, p-dibromide benzyl (0.5g, 0.0018mol) was added dropwise to the above system, and the reaction was stirred at room temperature for 7 hours. Obtaining a macroinitiator C1 solution;
(3) styrene monomer (19g, 0.18mol) was added to the macroinitiator C1 solution described in step b and reacted at 75 ℃ for 10 hours under an inert atmosphere. After the reaction is finished, dropwise adding the solution into absolute ethyl alcohol for precipitation, and filtering and separating. Dissolving the product with benzene, precipitating the product in ethanol for three times, vacuum-drying the product at 50 ℃ for 10 hours, and then vacuum-drying the product at 85 ℃ overnight to obtain the target product: p1. The yield was 84%.
Example 2: preparation of P2
The preparation method comprises the following specific steps: the preparation method comprises the following specific steps: the same portions as those in example 1 are not described in detail, and the difference from example 1 is that the molar ratio of the macroinitiator to the monomer styrene is 1: 300.
Example 3: preparation of P3
The preparation method comprises the following specific steps: the same portions as those in example 1 are not described again, and the difference from example 1 is that the molar ratio of the macroinitiator to the monomer is 1: 500.
Example 4: preparation of P4
The preparation method comprises the following specific steps: the same portions as those in example 1 are not repeated, and the difference from example 1 is that the molar ratio of dicarboxylic acid azo initiator and dibromide benzyl used for synthesizing the macroinitiator is 1: 1.2, and the molar ratio of macroinitiator and monomer styrene is 1: 300.
Example 5: preparation of P5
The preparation method comprises the following specific steps: the same portions as those in example 1 are not described again, and the difference from example 1 is that the molar ratio of the dicarboxylazo compound and the dibromobenzyl compound used for synthesizing the macroinitiator is 1: 1.4, and the molar ratio of the macroinitiator to the monomer styrene is 1: 300.
Example 6: preparation of P6
The preparation method comprises the following specific steps: the same parts as those in example 1 are not repeated, and the difference from example 1 is that the molar ratio of the azobiscyanovaleric acid to p-dibromobenzyl used for synthesizing the macroinitiator is 1.2: 1, and the molar ratio of the macroinitiator to the monomer styrene is 1: 300.
Example 7: preparation of P7
The preparation method comprises the following specific steps: the same parts as those in example 1 are not repeated, and the difference from example 1 is that the molar ratio of the azobiscyanovaleric acid to p-dibromobenzyl used for synthesizing the macroinitiator is 1.4: 1, and the molar ratio of the macroinitiator to the monomer styrene is 1: 300.
Hereinafter, the degradable polystyrene and the preparation method thereof according to the present invention will be further explained with reference to some of the results of examples.
TABLE 1 significant variation in viscosity average molecular weight for different initiator to monomer ratios
| Polymer and method of making same | Azobiscyanovaleric acid/p-dibromide/styrene (molar ratio) | Viscosity average molecular weight |
| P1 | 1/1/100 | 108465 |
| P2 | 1/1/300 | 41786 |
| P3 | 1/1/500 | 25803 |
| P4 | 1/1.2/300 | 37569 |
| P5 | 1/1.4/300 | 30876 |
| P6 | 1.2/1/300 | 39645 |
| P7 | 1.4/1/300 | 33864 |
Table 1 shows that the viscosity average molecular weight of P1-P3 is obviously changed under the conditions of different ratios of the initiator to the monomer, the viscosity average molecular weight is reduced along with the reduction of the ratio of the initiator to the monomer under the same reaction condition, the molar ratio of the azodicyano valeric acid used for synthesizing the macroinitiator to the dibromobenzyl is changed, the molecular weight of the polymer is influenced to a certain extent, and the molecular weight of the polymer is gradually reduced along with the increase of the excess degree. The molecular weight of the polymer can be regulated and controlled by changing the ratio of the reaction initiator to the monomer, so that the polystyrene with the required molecular weight is obtained.
TABLE 2 degradation rate of P1 before and after reaction in aqueous sodium hydroxide solution
| Degradation time/h | Percent of degradation/%) |
| 2 | 32.4 |
| 4 | 44.6 |
| 6 | 51.9 |
| 8 | 53.7 |
Table 2 shows that the viscosity average molecular weight of P1 is obviously changed from 108465 to 50241 before and after the P1 reacts in the sodium hydroxide aqueous solution, and the degradation property is very obvious, which indicates that the degradable polystyrene provided by the invention has the characteristic of chemical degradation. Among them, the ester group in the structure plays a very critical role. In an alkaline solution, ester groups in the copolymer are continuously decomposed, polymer molecular chains are broken, one molecular chain is broken into a plurality of low-molecular-weight polystyrene sections, and the more ester groups in the molecular chain, the smaller the molecular weight of the polystyrene section formed after degradation.
TABLE 3 melt flowability of degradable polystyrene
| Polymer and method of making same | MFR(5000g/10min) |
| P1 | 19.29 |
| P2 | 25.71 |
| P3 | 38.57 |
| P4 | 35.64 |
| P5 | 36.47 |
| P6 | 33.69 |
| P7 | 34.54 |
| PS | 22.94 |
Table 3 shows that the degradable polystyrene provided by the invention has good melt flowability. Compared with pure polystyrene, the introduction of the ester group obviously increases the melt fluidity of the degradable polystyrene, and is more beneficial to processing and molding.
FIG. 1 shows NMR of p-dibromide benzyl, macroinitiator and degradable polystyrene1And H, spectrum. As can be seen from the figure, the chemical environment of a (chemical shift of 4.56ppm) hydrogen in p-dibrominated benzyl changed due to the formation of an ester group, and the chemical shift of methylene hydrogen in C1 shifted to 5.10 ppm. b hydrogen is acted on by ester and methyl, chemical positionThe shift to 1.95ppm also predicts a match, confirming the successful synthesis of the macroinitiator containing an ester group. Peaks at 2.10ppm and 2.98ppm in P1 were assigned to the solvent N, N-dimethylacetamide, and peaks at 1.18ppm and 3.59ppm were assigned to the poor solvent ethanol. The blunt resonance absorption peak at 7.23ppm is attributed to the benzene rings on polystyrene, while the peak between 0.8 and 2.5ppm is attributed to the hydrogen on the polystyrene backbone. These are all in agreement with the predicted results, demonstrating that the monomers are successfully polymerized under the action of the initiator to form the ester-based multi-block polystyrene.
FIG. 2 is a DSC chart of P1, P7, PS, showing that the glass transition temperature of P1 is 85.2 deg.C, the glass transition temperature of P7 is 84.9 deg.C, the glass transition temperature of the polystyrene standard is 92.8 deg.C, and showing that the introduction of ester groups increases the flexibility of the polymer backbone and thus has a lower glass transition temperature compared to pure polystyrene. These results also match the melt index test data.
Therefore, the degradable polystyrene provided by the invention has good degradation performance, lower glass transition temperature, good melt flowability and hot-working performance. The main raw materials are industrial products, the one-pot reaction is easy for industrial production, and the industrial application of the degradable styrene polymer is favorably realized. The method can be used for synthesizing polystyrene and copolymers thereof, and can also be popularized and applied to the synthesis of other polymers.
Claims (7)
1. A degradable polystyrene having a structure represented by formula I:
wherein,
R1represents:
R2represents:
R3represents:
m and n represent: the number of the structural units in the degradable polystyrene chain segment is repeated.
2. The degradable polystyrene of claim 1, wherein: the degradable polystyrene structure contains one or more of ester group, o-nitrobenzyl ester or disulfide group.
3. The method for preparing a degradable polystyrene as claimed in claim 1, wherein: the method comprises the following steps:
wherein, X represents: -Br, -Cl or-I,
(1) adding a dihalogen compound, a dicarboxylic acid initiator and an organic base into a solvent, and reacting at room temperature to obtain a macromolecular initiator solution;
(2) mixing the macromolecular initiator solution obtained in the step (1) with a styrene monomer under an inert atmosphere to react at 75 ℃ to obtain an ester-based multi-block polystyrene solution;
(3) and (3) dropwise adding the solution obtained in the step (2) into a poor solvent, filtering, washing and drying to obtain the target polymer.
4. The method for preparing degradable polystyrene as claimed in claim 3, wherein: in the step (1), the dicarboxylic acid initiator and the organic base are mixed in an ice-water bath.
5. The method for preparing degradable polystyrene as claimed in claim 3, wherein: the organic base in the step (1) is one or more of tetramethylguanidine, 1, 8-diazabicycloundec-7-ene, sodium ethoxide, sodium methoxide, potassium tert-butoxide and alkyl lithium.
6. The method for preparing degradable polystyrene as claimed in claim 3, wherein: the mass ratio of the macroinitiator solution to the styrene monomer in the step (2) is 1: 100-1: 500.
7. The method for preparing degradable polystyrene as claimed in claim 3, wherein: the drying temperature in the step (3) is 35-90 ℃.
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| CN113621095A (en) * | 2021-08-30 | 2021-11-09 | 南京工程学院 | Degradable polymer initiator and preparation method thereof |
| CN114957573A (en) * | 2022-07-08 | 2022-08-30 | 王兵 | Synthetic method of degradable polystyrene containing nitrobenzyl disulfide and o-nitrobenzyl ester blocks |
| CN115141297A (en) * | 2022-07-07 | 2022-10-04 | 李旭东 | Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular azo initiator |
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| CN112121862A (en) * | 2020-10-15 | 2020-12-25 | 江西赣江新区有机硅创新研究院有限公司 | Magnetic immobilized platinum catalyst and preparation method and application thereof |
| CN113621095A (en) * | 2021-08-30 | 2021-11-09 | 南京工程学院 | Degradable polymer initiator and preparation method thereof |
| CN115141297A (en) * | 2022-07-07 | 2022-10-04 | 李旭东 | Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular azo initiator |
| CN115141297B (en) * | 2022-07-07 | 2024-02-20 | 广东蓝海包装新技术有限公司 | Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular azo initiator |
| CN114957573A (en) * | 2022-07-08 | 2022-08-30 | 王兵 | Synthetic method of degradable polystyrene containing nitrobenzyl disulfide and o-nitrobenzyl ester blocks |
| CN114957573B (en) * | 2022-07-08 | 2024-06-07 | 中山市金博包装材料有限公司 | Synthesis method of degradable polystyrene containing nitrobenzyl disulfide and o-nitrobenzyl ester block |
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