CN109928879A - A kind of acrylate carbonic ester and its homopolymer and copolymer material - Google Patents
A kind of acrylate carbonic ester and its homopolymer and copolymer material Download PDFInfo
- Publication number
- CN109928879A CN109928879A CN201910165505.6A CN201910165505A CN109928879A CN 109928879 A CN109928879 A CN 109928879A CN 201910165505 A CN201910165505 A CN 201910165505A CN 109928879 A CN109928879 A CN 109928879A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- carbonic ester
- ester
- reaction
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of acrylate carbonic ester and its homopolymers and copolymer material.Steps are as follows for acrylate carbonic ester preparation method: 1) in a high pressure reaction kettle, acrylate is uniformly mixed in solvent-free or organic solvent with alkali catalyst, is passed through carbon dioxide and is reacted, and obtains carbonic acid monoesters intermediate；2) alkyl halide is added into the autoclave of step 1), is passed through carbon dioxide reaction, separating-purifying obtains acrylate carbonic ester after reaction.The characteristics of present invention has technological operation simple and easy, low in cost, is suitable for industrialized production, acrylate carbonic ester preparation process of the invention is simple and efficient, and the regulation to acrylate structural carbonate may be implemented by the alkyl halide for choosing different；The homopolymer and its copolymer of acrylate carbonic ester of the invention have fluorophor, can be used for fluorescent paint.
Description
Technical field
The present invention relates to a kind of carbonic ester and its homopolymer and copolymer material, especially a kind of acrylate carbonic ester and
Its homopolymer and copolymer material.
Background technique
Polycarbonate is a kind of engineering plastics, and high comprehensive performance shows that its rigidity and elasticity modulus are high, and heat is steady
Qualitative good, the good transparency, creep resistance outstanding, electrical insulating property, weatherability, its shock resistance is strong under identical use condition
Degree is higher than Other Engineering plastics.Polycarbonate is many kinds of, can be divided into fatty poly-ester carbonate, alicyclic according to its design feature
Polycarbonate, aromatic copolycarbonate and aliphatic-aromatic adoption carbonic ester.
The preparation of polycarbonate can use polycondensation, the ring-opening polymerisation and ring-type of epoxide and carbon dioxide at present
The ring-opening polymerisation of carbonic ester.The polycondensation of bisphenol-A and phosgene is the classical synthetic method of industrial polycarbonate, including solution polycondensation
With two kinds of approach of interfacial polycondensation, but phosgene has severe toxicity and is not easy to quantitative, while the molecular weight of polycarbonate is smaller, development
It is restricted.The some drawbacks of phosgene can be overcome instead of phosgene using triphosgene, the invention of Publication No. CN1603353A is special
Benefit is reported using triphosgene and bisphenol-A as raw material, and molar ratio 1:0.3-0.5 is deposited in phase transfer catalyst, tertiary amine and chain extender
Under, ultra high molecular-weight polycarbonate has been obtained by polycondensation, washing, sedimentation and a separation unit process.
Transesterification is carried out using dihydric alcohol and binary alkyl carbonic ester and prepares polycarbonate, generallys use basic catalyst,
It is polymerize at 120-150 DEG C, ester interchange polymerization can regulate and control polycarbonate by choosing the dihydric alcohol of different structure
Structural behaviour, polymerization technique is simple, environmentally protective, has preferable industrial prospect.DirkKuckling etc. is with 1,4- dioxy
Six rings are solvent, and 4- dimethylamino pyridine or acetylacetone,2,4-pentanedione lithium are catalyst, and the glycol of different structure is pressed with dimethyl carbonate
According to the feed ratio of equimolar amounts, transesterification polymerization, is prepared for line style and hyperbranched polycarbonate under the conditions of normal pressure and 120 DEG C
Material, wherein linear polycarbonate can be stabilized (RSC Adv., 2017,7,12550) under acid and weak basic condition.
Polycarbonate is prepared compared with traditional phosgene route, utilizes the ring-opening polymerisation approach of epoxide and carbon dioxide
It is considered more environmentally-friendly green, meets the requirement of sustainable development.Common epoxy monomer include: ethylene oxide, propylene oxide,
Epoxy butane, cyclohexene oxide, styrene oxide.The electron donation of epoxide monomer substituent is stronger, and polymerization is lived
Property is bigger, but the reactivity of carbon dioxide is relatively low, it is necessary to seek high activity and highly selective catalyst, this respect has drawn
The research interest for playing numerous scholars, has been developed based on the various efficient catalytics of zinc, aluminium, chromium, cobalt and bimetal complexes at present
System.(Chem.Soc.Rev.2012,41,1462–1484).Holger Frey etc. is in cobalt complex and bis- (triphenylphosphine) chlorine
Change in the dual catalyst system that imonium is constituted, realizes carbon dioxide and propylene oxide (PO), lauryl diglycidyl ether (DDGE)
Copolymerization, be prepared for side chain be long-chain glycidol ether structure polycarbonate can be controlled by adjusting the ratio of PO and DDGE
Polycarbonate processed is from the unformed transformation (Macromol.Rapid Commun.2018,39,1800558) to semicrystalline.
High-molecular-weight polycarbonate can be prepared using the ring-opening polymerisation of cyclic carbonate ester monomer, common monomer includes five yuan
The big cyclic carbonate ester monomer of cyclic carbonate ester, hexa-atomic cyclic carbonate ester, heptatomic ring carbonic ester and seven yuan or more.Above-mentioned monomer is in difference
Under initiator and catalyst action, it can be realized and be opened by cationic mechanism, anionic mechanism, coordination mechanism and enzymatic mechanism
Cyclopolymerization, to obtain the specific polycarbonate of structure or the oligomer with active side chain, active end group
(Prog.Polym.Sci.2000,25,259–342).Takeshi Endo etc. selects diphenyl carbonate to replace traditional triphosgene
Or phosgene, it is reacted respectively with neopentyl glycol and two (trimethylolpropanes), is efficiently synthesized out single hexa-atomic cyclic carbonate ester (NPGC)
And double hexa-atomic cyclic carbonate ester (DTMPC) monomers, cause single hexatomic ring carbonic acid alicyclic monomer ring-opening polymerisation with the ethanol amine of different structure,
Prepare the line style containing tertiary amine structure, distant pawl, star-like polycarbonate；Under ethanol amine initiation open loop occurs for NPGC and DTMPC
Copolymerization, prepares amido modified high-molecular-weight polycarbonate film, has transparency height, the good feature of flexibility, and pass through
Further alkylated reaction is converted into the film of quaternary ammonium salt functionalization.(J Polym.Sci.Pol.Chem.,2016,54(4):
487-497)。
Makrolon material is due to its superior performance, in electronic apparatus, automobile, illumination, instrument, optics, building materials, packaging
It all occupies a tiny space with fields such as small stores, according to actual needs, design structure is novel, has excellent performance, preparation method
The makrolon material being simple and efficient is conducive to the sustainable development of polycarbonate industry.Tradition prepares the method for polycarbonate all
To form carbonate functionalities on main chain during polymerization, the invention patent novelty propose first to olefinic monomer into
Row carbonic ester functional modification, later again polymerize alkene, prepares polycarbonate of the carbonate functional in side group.
Polymethacrylates is important one of general-purpose plastics, and wherein polymethyl methacrylate is used as " organic glass "
Articles and dental material already exceed over half a century, although its mechanical performance is lower than common engineering plastics, in translucency, dress
Decorations property aspect has unique distinction, and a kind of engineering plastics kind has been used as to be widely used in industry and transportation etc..Function
Energy property polymethacrylate material is widely used in the fields such as chemistry and biology, by the favor of researcher, there is two at present
Kind of approach can prepare functional polyalkylene methacrylate: a kind of approach is the poly- methyl for first preparing certain molecular weight and dispersion degree
Acrylate is grafted upper functional groups by chemical modification later；Another way is first to synthesize functional methacrylic acid
Ester monomer prepares functional polyalkylene methacrylate by homopolymerization or copolymerization later.The first approach needs two steps or multi-step
Process, preparation process is cumbersome, and the position of the functional group of grafting up and quantity are difficult to control；Second of approach preparation process
It is relatively easy, it is the common method for preparing functional polyalkylene methacrylate, key is functional methacrylate monomers
Structure design and efficiently synthesize, it has also become the research emphasis in the field.
The invention patent contains carbonic acid by the reversible addition building of acrylic acid hydroxy alkyl ester and carbon dioxide in the presence of highly basic
The acrylate monomer derivative of ester group prepares polyacrylate carbonic ester and its copolymer material by homopolymerization or copolymerization later
Material, has not been reported at present.
Summary of the invention
The object of the present invention is to provide a kind of acrylate carbonic ester and its homopolymers and copolymer material.The present invention
It is simple and easy with technological operation, it is low in cost, be suitable for industrialized production the characteristics of.
Technical solution of the present invention: a kind of acrylate carbonic ester, structural formula are as follows:
Wherein y=0-5；R1For one of H, methyl or ethyl；R2For one of following functional group:
Aliphatic functionality:
Heterocycle functional group:
Aromatic functional groups:
Acrylate carbonic ester above-mentioned, is prepared via a method which:
1) in a high pressure reaction kettle, acrylic acid hydroxy alkyl ester mixes in solvent-free or organic solvent with alkali catalyst
It is even, it is passed through carbon dioxide and reacts, obtain carbonic acid monoesters intermediate；
2) alkyl halide is added into the autoclave of step 1), is passed through carbon dioxide reaction, separation mentions after reaction
Pure acquisition acrylate carbonic ester.
Acrylate carbonic ester above-mentioned, acrylic acid hydroxy alkyl ester includes acrylate, acrylic acid in the method
Hydroxyl ethyl ester, hydroxypropyl acrylate, hy-droxybutyl, the own ester of acrylic acid hydroxyl, hydroxy methyl methacrylate, hydroxyethyl methacrylate second
The own ester of ester, hydroxy propyl methacrylate, methacrylate, hydroxyethyl methacrylate, ethylacrylic acid hydroxyl methyl esters, ethyl third
Olefin(e) acid hydroxyl ethyl ester, ethylacrylic acid hydroxypropyl acrylate, ethylacrylic acid hydroxy butyl ester and the own ester of ethylacrylic acid hydroxyl.
Acrylate carbonic ester above-mentioned, highly basic includes organic base and inorganic base in the method, and organic base includes 1,1,
3,3- tetramethylguanidine, 11 carbon -7- alkene of 1,8- diazabicylo, bicyclic (4.4.0) the decyl- 5- alkene of tri- nitrine of 1,5,7-, triethylamine,
Diethylamine, 4- dimethylamino pyridine, pyrrolidines and piperidines and pyridine；Inorganic base includes cesium carbonate, potassium carbonate, potassium tert-butoxide, hydrogen
Potassium oxide and sodium hydroxide；The dosage of highly basic and the molar ratio of acrylic acid hydroxy alkyl ester are as follows: 0.1-4:1.
Acrylate carbonic ester above-mentioned, the organic solvent in the method are dimethyl sulfoxide, N, N- dimethyl formyl
Amine, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, acetonitrile or toluene；When using organic solvent, acrylic acid hydroxy alkyl ester exists
Concentration control in organic solvent is 0.5-5mol/L.
Acrylate carbonic ester above-mentioned, in the step 1), the pressure for being passed through reaction kettle after carbon dioxide is maintained
0.1-6MPa, reaction temperature is at 25-100 DEG C, and the reaction time is in 0.5-24h.
Acrylate carbonic ester above-mentioned, the step 2) alkyl halide includes following compound:
Aliphatic alkyl halide:
Heterocycle alkyl halide:
Aromatic alkyl halide:
Acrylate carbonic ester above-mentioned, the additional amount of alkyl halide and mole of acrylic acid hydroxy alkyl ester described in step 2)
Than being added including original position and being added after pressure release for the mode of 1-3:1, addition, it is passed through the pressure of the carbon dioxide in autoclave
Maintain 0.1-6MPa, reaction temperature at 25-100 DEG C, the reaction time in 0.5-72h, after reaction by vacuum distillation or
Silica gel column chromatography separating-purifying obtains acrylate carbonic ester.
A kind of homopolymer material of acrylate carbonic ester above-mentioned preparation, be using acrylate carbonic ester as monomer, into
It is made after row homopolymerization, structural formula is as follows:
Wherein n is average degree of polymerization, 1≤n≤1000；Y indicates the number of methylene, y=0-5；R1For H, methyl or second
One of base；R2For one of following functional group:
Aliphatic functionality:
Heterocycle functional group:
Aromatic functional groups:
A kind of copolymer material of acrylate carbonic ester preparation above-mentioned, is with acrylate carbonic ester and R3Group is made
For monomer, it is made after carrying out copolyreaction, wherein R3Group includes vinyl monomer and diolefinic monomer, wherein vinyl monomer
It include: ethylene, propylene, vinyl chloride, vinylidene chloride, propenyl, acrylamide, methacrylic acid, methyl methacrylate, third
E pioic acid methyl ester, ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, acrylic acid-2-ethyl caproite, acrylonitrile, styrene, α-
Methyl styrene, vinylacetate, methyl vinyl ether, vinyl pyrrolidone, maleic acid, maleic anhydride, itaconic acid,
Norbornene and cyclohexene；Diolefinic monomer includes: butadiene, chlorobutadiene, pentadiene, isoprene and cyclopentadiene.
Beneficial effects of the present invention
The advantages of present invention has technological operation simple and easy, low in cost, is suitable for industrialized production.Of the invention third
Olefin(e) acid ester carbonic ester preparation process is simple and efficient, and may be implemented by the alkyl halide for choosing different to acrylate structural carbonate
Regulation；The homopolymer and its copolymer of acrylate carbonic ester of the invention have fluorophor, can be used for fluorescent paint.
Detailed description of the invention
Fig. 1 is the structural formula of acrylate carbonate copolymer material of the present invention；
Fig. 2 is the acrylate carbonate products cross reference to related application nucleus magnetic hydrogen spectrum that embodiment 1 synthesizes；
Fig. 3 is the acrylate carbonate products cross reference to related application nuclear-magnetism carbon spectrum that embodiment 1 synthesizes；
Fig. 4 is polyacrylate carbonate products cross reference to related application nucleus magnetic hydrogen spectrum prepared by embodiment 8；
Fig. 5 is polyacrylate carbonate products cross reference to related application nuclear-magnetism carbon spectrum prepared by embodiment 8；
Fig. 6 is polyacrylate carbonate products cross reference to related application thermal multigraph prepared by embodiment 8；
Fig. 7 is polyacrylate carbonate products cross reference to related application DSC figure prepared by embodiment 8.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
Embodiment 1
N,N-dimethylformamide (DMF, 20mL), hydroxyethyl methacrylate are added into 50mL autoclave
(50mmol), 1,1,3,3- tetramethylguanidine (TMG, 50mmol) are passed through carbon dioxide and stablize to 1MPa, be placed in 30 DEG C of oil bath pans
Benzyl bromine (55mmol) is added from charge pipe in situ in reaction 1 hour, is passed through carbon dioxide and stablizes to 2MPa, is placed in 30 DEG C of oil baths
It is reacted 24 hours in pot, is filtered to remove salt after reaction, be extracted with ethyl acetate after being dissolved in water three times, merged organic phase and use
Anhydrous sodium sulfate is dry, is later that eluant, eluent is obtained by silica gel column chromatography separating-purifying with petrol ether/ethyl acetate=10:1
Target product, yield 78%.1H NMR(400MHz,CDCl3) δ 7.37 (dd, J=8.6,3.4Hz, 5H), 6.12 (s, 1H),
5.58 (d, J=1.6Hz, 1H), 5.30 (s, 1H), 5.18 (s, 2H), 4.39 (ddd, J=6.0,3.7,1.4Hz, 4H), 1.93
(s,3H).13C NMR(101MHz,CDCl3)δ166.89,154.87,135.71,135.03,128.50,128.48,
128.26,128.24,126.07,69.68,65.53,62.22,18.11.
Influence of the different organic solvents to reaction is compared under the same conditions, as shown in table 1, the results showed that, use is molten
Agent is conducive to the raising of products collection efficiency, the yield of target product relatively low (table 1, the number 5,6), in polarity in low polar solvent
More satisfactory yield can be obtained in aprotic solvent, wherein best as the effect of reaction dissolvent using n,N-Dimethylformamide
(table 1, number 1)；Using DMF as solvent, the effect of different catalysts is compared under the same conditions, the results showed that organic base is urged
Change effect and be better than inorganic base (table 1, number 1,8-12), wherein the catalytic effect of 1,1,3,3- tetramethylguanidine is best；Identical
CO has been investigated under reaction condition2Influence (table 1, number 1,13-17) of the pressure to reaction, is as a result indicated with pressure carbon dioxide
Raising, the yield of target product is in increase trend, and when reaching 2MPa, yield reaches maximum value, further increases pressure yield
It is declined slightly；Under the same reaction conditions, also there is increased trend (table with the extension of reaction time in the yield of target product
1, number 1,18-20), there is no increase for yield after reaction 24 hours；Further experiment shows the raising with reaction temperature,
Downward trend (table 1, number 1,21-24) is presented in yield.
Table 1: the influence of differential responses condition acrylate carbonic acid Lipase absobed
Embodiment 2
N,N-dimethylformamide (DMF, 20mL), hydroxyethyl methacrylate are added into 50mL autoclave
11 carbon -7- alkene (DBU, 50mmol) of (50mmol), 1,8- diazabicylo is passed through carbon dioxide and stablizes to 0.5MPa, is placed in
It is reacted 0.5 hour in 50 DEG C of oil bath pans；Carbon dioxide is discharged after stopping reaction, opens reaction kettle, 4- trifluoromethyl benzyl bromine is added
(60mmol) is passed through carbon dioxide and stablizes to 3MPa, be placed in 50 DEG C of oil bath pans and react 6 hours, be filtered to remove after reaction
Salt is extracted with ethyl acetate three times after being dissolved in water, and merges organic phase anhydrous sodium sulfate drying, uses petroleum ether/acetic acid later
Ethyl ester=6:1 be eluant, eluent by silica gel column chromatography separating-purifying obtain target product, yield 76%,1H NMR(600MHz,
CDCl3) δ 7.62 (d, J=8.1Hz, 1H), 7.50 (d, J=8.0Hz, 1H), 6.10 (s, 1H), 5.57 (s, 1H), 5.22 (s,
1H),4.44–4.40(m,1H),4.39–4.35(m,1H),1.92(s,2H).13C NMR(101MHz,CDCl3)δ167.14,
154.91,139.11,135.82,128.34,126.38,125.70,125.66,68.79,65.97,62.30,18.31.
Embodiment 3
N,N-dimethylformamide (DMF, 20mL), hydroxyethyl methacrylate are added into 50mL autoclave
Bicyclic (4.4.0) the decyl- 5- alkene (TBD, 50mmol) of (50mmol), tri- nitrine of 157- is passed through carbon dioxide and stablizes to 2MPa, be placed in
It is reacted 3 hours in 40 DEG C of oil bath pans；4- trifluoromethoxy benzyl bromine (70mmol) is added from charge pipe in situ, is passed through carbon dioxide
Stablize to 4MPa, be placed in 40 DEG C of oil bath pans and react 72 hours, be filtered to remove salt after reaction, acetic acid second is used after being dissolved in water
Ester extracts three times, merges organic phase anhydrous sodium sulfate drying, is later that eluant, eluent passes through with petrol ether/ethyl acetate=6:1
Silica gel column chromatography separating-purifying acquisition target product, yield 53%,1H NMR(600MHz,CDCl3) δ 7.42 (d, J=
8.4Hz, 2H), 7.21 (d, J=8.3Hz, 2H), 6.10 (s, 1H), 5.57 (s, 1H), 5.16 (s, 2H), 4.41 (dd, J=
6.0,3.2Hz, 2H), 4.37 (dd, J=6.0,3.3Hz, 2H), 1.92 (s, 3H)13C NMR(101MHz,CDCl3)δ
167.13,154.93,149.39,149.37,135.83,133.86,130.02,126.34,121.20,121.19,121.18,
121.17,68.85,65.86,62.32,18.29.
Embodiment 4
N,N-dimethylformamide (DMF, 20mL), hydroxyethyl methacrylate are added into 50mL autoclave
(50mmol), cesium carbonate (Cs2CO3, 150mmol), it is passed through carbon dioxide and stablizes to 1MPa, it is small to be placed in reaction 1 in 30 DEG C of oil bath pans
When；Bromination of n-butane (55mmol) is added from charge pipe in situ, is passed through carbon dioxide and stablizes to 3MPa, be placed in 30 DEG C of oil bath pans
Middle reaction 24 hours, is filtered to remove salt after reaction, is extracted with ethyl acetate three times after being dissolved in water, merges organic phase nothing
Aqueous sodium persulfate is dry, is later that eluant, eluent passes through silica gel column chromatography separating-purifying acquisition target with petrol ether/ethyl acetate=6:1
Product, yield 70%,1H NMR(400MHz,CDCl3) δ 6.48 (d, J=2Hz, 1H), 6.50 (d, J=2Hz, 1H), 4.39
(s,2H),4.38(s,2H),4.21(s,2H),2.01(s,3H),1.62(s,2H),1.45(s,2H),0.9(s,3H).13C
NMR(101MHz,CDCl3)δ167.2,155.5,136.0,125.7,69.2,67.8,62.5,30.8,19.3,18.5,17.2.
Embodiment 5
N,N-dimethylformamide (DMF, 20mL), hy-droxybutyl are added into 50mL autoclave
(50mmol), 1,1,3,3- tetramethylguanidine (TMG, 50mmol) are passed through carbon dioxide and stablize to 1MPa, be placed in 30 DEG C of oil bath pans
Bromomethyl furans (55mmol) is added from charge pipe in situ in reaction 1 hour, is passed through carbon dioxide and stablizes to 3MPa, is placed in 30
It is reacted 24 hours in DEG C oil bath pan, is filtered to remove salt after reaction, is extracted with ethyl acetate three times, is associated with after being dissolved in water
Machine is mutually dry with anhydrous sodium sulfate, is later that eluant, eluent is separated by silica gel column chromatography and mentioned with petrol ether/ethyl acetate=10:1
Pure acquisition target product, yield 65%.1H NMR(400MHz,CDCl3)δ7.55(s,1H),6.42(s,2H),6.12(s,
1H), 5.58 (d, J=1.6Hz, 1H), 5.30 (s, 1H), 5.15 (s, 2H), 4.26 (t, J=2Hz, 2H), 3.92 (t, 2H),
1.66-1.62(m,4H).13C NMR(101MHz,CDCl3)δ166.7,158.3,150.3,147.2,133.2,128.3,
110.7,107.5,65.0,62.9,69.0,26.3,21.5.
Embodiment 6
Monomer (10mmol) is added into Xi Laike bottles, is dissolved with 2mL tetrahydrofuran, leading to nitrogen displacement, addition is even afterwards three times
Nitrogen bis-isobutyronitrile (2.5mol%) is placed in 70 DEG C of oil bath pans under nitrogen protection and reacts 24 hours, pours into 10mL after reaction
Precipitating is precipitated in cold methanol, is washed (10mL × 3) three times with methanol, is dried in vacuo, yield 94%,1H NMR(400MHz,
CDCl3) δ 7.38-7.27 (m, 5H), 5.11 (s, 2H), 4.15 (d, J=44.2Hz, 4H), 1.82 (d, J=32.2Hz, 2H),
0.94 (d, J=53.6Hz, 3H)13C NMR(101MHz,)δ176.73,176.01,154.72,135.08,128.47,
128.20,69.56,64.91,62.31,44.92,44.57,18.51,16.68. number-average molecular weights are as follows: 81000, dispersibility refers to
Number: 1.71, glass transition temperature: 6 DEG C, initial decomposition temperature are as follows: 216 DEG C.
Embodiment 7
Monomer (10mmol) is added into Xi Laike bottles, is dissolved with 2mL methylene chloride, logical nitrogen displacement was added afterwards three times
It aoxidizes dibenzoyl (1mol%), is placed in 70 DEG C of oil bath pans under nitrogen protection and reacts 24 hours, pour into 15mL after reaction
Precipitating is precipitated in cold ethyl alcohol, three times (15mL × 3) with ethanol washing, vacuum drying, yield 90%,1H NMR(600MHz,
CDCl3) δ 7.57 (d, J=7.8Hz, 2H), 7.43 (d, J=7.3Hz, 2H), 5.15 (s, 2H), 4.26 (d, J=14.8Hz,
2H),4.12(s,2H),2.03–1.72(m,2H),1.08–0.76(m,3H).13C NMR(101MHz,CDCl3)δ154.73,
139.20,128.25,125.58,125.54,68.64,67.93,65.25,62.42,45.0 4,44.71,25.58. number is divided equally
Son amount are as follows: 105300, monodispersity index: 1.98, glass transition temperature: 4 DEG C, initial decomposition temperature are as follows: 293 DEG C.
Embodiment 8
Monomer (10mmol) is added into Xi Laike bottles, is dissolved with 2mL tetrahydrofuran, leading to nitrogen displacement, addition is even afterwards three times
Nitrogen bis-isobutyronitrile (2mol%), trithiocarbonate RAFT reagent are placed in 70 DEG C of oil bath pans under nitrogen protection and react 24 hours,
It pours into after reaction and precipitating is precipitated in 20mL cold isopropanol, washed (20mL × 3) three times with isopropanol, is dried in vacuo, yield
89%,1H NMR(600MHz,CDCl3) δ 7.37 (d, J=8.2Hz, 2H), 7.17 (d, J=7.9Hz, 2H), 5.10 (s, 2H),
4.24 (s, 2H), 4.12 (s, 2H), 1.85 (t, J=36.7Hz, 2H), 1.07-0.78 (m, 3H)13C NMR(101MHz,
CDCl3)δ154.84,154.81,149.27,149.25,133.96,129.97,129.96,124.29,121.73,121.12,
119.17,116.61,68.74,65.17,62.45,44.77,18.60,16.86. number-average molecular weights are as follows: 141000, dispersibility
Index: 1.10, glass transition temperature: -6 DEG C, initial decomposition temperature are as follows: 302 DEG C.
Embodiment 9
Monomer 1 (10mmol) and monomer 2 (methyl methacrylate, 5mmol) are added into Xi Laike bottles, with 5mL tetrahydro
Furans dissolution leads to nitrogen displacement and dibenzoyl peroxide (1.5mol%) is added afterwards three times, is placed in nitrogen in 80 DEG C of oil bath pans and protects
It shield lower reaction 24 hours, pours into precipitating is precipitated in 20mL cold methanol after reaction, wash (20mL × 3) three times with methanol, very
Sky is dry, yield 86%,1H NMR(400MHz,CDCl3)δ7.33(s,2H),7.30(s,1H),7.27(s,1H),5.26(s,
2H),4.39-4.36(m,4H),3.9(s,3H),2.35-2.33(m,1H),2.23-2.20(m,2H),2.15(1H),1.20-
1.16(m,4H),1.12(s,3H).13C NMR(101MHz,CDCl3)δ173.1,171.5,158.2,136.2,128.5,
127.6,126.5,71.2,68.3,62.5,52.3,42.3,36.5,32.5,30.4,21.8,17.5. number-average molecular weight are as follows:
112000, monodispersity index: 1.76, glass transition temperature: 3 DEG C, initial decomposition temperature are as follows: 263 DEG C.
2 acrylate carbonic ester hot property of table
Claims (10)
1. a kind of acrylate carbonic ester, which is characterized in that its structural formula is as follows:
Wherein y=0-5；R1For one of H, methyl or ethyl；R2For one of following functional group:
Aliphatic functionality:
Heterocycle functional group:
Aromatic functional groups:
2. acrylate carbonic ester according to claim 1, which is characterized in that be prepared via a method which:
1) in a high pressure reaction kettle, acrylic acid hydroxy alkyl ester is uniformly mixed in solvent-free or organic solvent with alkali catalyst,
It is passed through carbon dioxide and reacts, obtain carbonic acid monoesters intermediate；
2) alkyl halide is added into the autoclave of step 1), is passed through carbon dioxide reaction, separating-purifying obtains after reaction
Obtain acrylate carbonic ester.
3. acrylate carbonic ester according to claim 2, it is characterised in that: acrylic acid hydroxy alkyl ester packet in the method
Include acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, the own ester of acrylic acid hydroxyl, methacrylic acid
The own ester of hydroxyl methyl esters, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylate, hydroxyethyl methacrylate, second
Base acrylate, ethylacrylic acid hydroxyl ethyl ester, ethylacrylic acid hydroxypropyl acrylate, ethylacrylic acid hydroxy butyl ester and ethylacrylic acid
The own ester of hydroxyl.
4. acrylate carbonic ester according to claim 2, it is characterised in that: in the method highly basic include organic base and
Inorganic base, organic base are bicyclic including 1,1,3,3- tetramethylguanidine, 1,8- diazabicylo, 11 carbon -7- alkene, 1,5,7- tri- nitrine
(4.4.0) decyl- 5- alkene, triethylamine, diethylamine, 4- dimethylamino pyridine, pyrrolidines and piperidines and pyridine；Inorganic base includes carbonic acid
Caesium, potassium carbonate, potassium tert-butoxide, potassium hydroxide and sodium hydroxide；The dosage of highly basic and the molar ratio of acrylic acid hydroxy alkyl ester are as follows:
0.1-4:1。
5. acrylate carbonic ester according to claim 2, it is characterised in that: the organic solvent in the method is diformazan
Base sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, acetonitrile or toluene；Using organic molten
When agent, the concentration control of acrylic acid hydroxy alkyl ester in organic solvent is 0.5-5mol/L.
6. acrylate carbonic ester according to claim 2, it is characterised in that: in the step 1), be passed through carbon dioxide
The pressure of reaction kettle maintains 0.1-6MPa afterwards, and reaction temperature is at 25-100 DEG C, and the reaction time is in 0.5-24h.
7. acrylate carbonic ester according to claim 2, it is characterised in that: the step 2) alkyl halide includes followingization
Close object:
Aliphatic alkyl halide:
Heterocycle alkyl halide:
Aromatic alkyl halide:
8. acrylate carbonic ester according to claim 2, it is characterised in that: the additional amount of alkyl halide described in step 2)
Molar ratio with acrylic acid hydroxy alkyl ester is 1-3:1, and the mode of addition includes that original position is added and is added after pressure release, and it is anti-to be passed through high pressure
Answer the pressure of the carbon dioxide in kettle to maintain 0.1-6MPa, reaction temperature at 25-100 DEG C, the reaction time in 0.5-72h, instead
Acrylate carbonic ester is obtained by vacuum distillation or silica gel column chromatography separating-purifying after answering.
9. a kind of homopolymer material of acrylate carbonic ester preparation according to claim 1-8, feature exist
In: be made after carrying out homopolymerization, structural formula is as follows using acrylate carbonic ester as monomer:
Wherein n is average degree of polymerization, 1≤n≤1000；Y indicates the number of methylene, y=0-5；R1For in H, methyl or ethyl
It is a kind of；R2For one of following functional group:
Aliphatic functionality:
Heterocycle functional group:
Aromatic functional groups:
10. a kind of copolymer material of acrylate carbonic ester preparation according to claim 1-8, feature exist
In: it is with acrylate carbonic ester and R3Group is made, wherein R as monomer after carrying out copolyreaction3Group includes vinyl
Monomer and diolefinic monomer, wherein vinyl monomer includes: ethylene, propylene, vinyl chloride, vinylidene chloride, propenyl, acryloyl
Amine, methacrylic acid, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, propylene
Acid -2- ethylhexyl, acrylonitrile, styrene, α-methylstyrene, vinylacetate, methyl vinyl ether, ethenyl pyrrolidone
Ketone, maleic acid, maleic anhydride, itaconic acid, norbornene and cyclohexene；Diolefinic monomer includes: butadiene, neoprene two
Alkene, pentadiene, isoprene and cyclopentadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910165505.6A CN109928879A (en) | 2019-03-05 | 2019-03-05 | A kind of acrylate carbonic ester and its homopolymer and copolymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910165505.6A CN109928879A (en) | 2019-03-05 | 2019-03-05 | A kind of acrylate carbonic ester and its homopolymer and copolymer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109928879A true CN109928879A (en) | 2019-06-25 |
Family
ID=66986516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910165505.6A Pending CN109928879A (en) | 2019-03-05 | 2019-03-05 | A kind of acrylate carbonic ester and its homopolymer and copolymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109928879A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115703789A (en) * | 2021-08-13 | 2023-02-17 | 四川大学 | Seven-membered cyclic carbonate monomer based on D-A reaction and preparation method of polycarbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084524A (en) * | 1992-03-06 | 1994-03-30 | 奈科姆成像有限公司 | The polymkeric substance that contains the oleophylic side group of biodegradable fracture |
| CN108117600A (en) * | 2017-12-24 | 2018-06-05 | 贵州大学 | The synthetic method of cellulose carbonate material and the application of cellulose carbonate material |
-
2019
- 2019-03-05 CN CN201910165505.6A patent/CN109928879A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084524A (en) * | 1992-03-06 | 1994-03-30 | 奈科姆成像有限公司 | The polymkeric substance that contains the oleophylic side group of biodegradable fracture |
| CN108117600A (en) * | 2017-12-24 | 2018-06-05 | 贵州大学 | The synthetic method of cellulose carbonate material and the application of cellulose carbonate material |
Non-Patent Citations (1)
| Title |
|---|
| MASASHI ISEKI等: "Design of a High-Performance Dismantlable Adhesion System Using Pressure-Sensitive Adhesive Copolymers of 2-Hydroxyethyl Acrylate Protected with tert -Butoxycarbonyl Group in the Presence of Cross-Linker and Lewis Acid", 《ACS OMEGA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115703789A (en) * | 2021-08-13 | 2023-02-17 | 四川大学 | Seven-membered cyclic carbonate monomer based on D-A reaction and preparation method of polycarbonate |
| CN115703789B (en) * | 2021-08-13 | 2024-04-26 | 四川大学 | Seven-membered cyclic carbonate monomer based on D-A reaction and preparation method of polycarbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109776773A (en) | A kind of preparation method of biodegradable block copolymer | |
| CN109776774B (en) | Phthalic anhydride and epoxy compound copolymerization and sequence control method | |
| EP0943641A1 (en) | Processes for the preparation of monodisperse polymers, processes for the continuous polymerization of cyclic monomers, and polymers prepared thereby | |
| CN105418835B (en) | A kind of preparation method of makrolon toughness reinforcing core shell structure acrylate-functional polymer particle | |
| CN105884987A (en) | Bi-sulfonate interface initiator and preparing method thereof | |
| CN110003481A (en) | A kind of preparation method of the miscellaneous arm star polymer of eight arms | |
| CN101543747B (en) | Method for preparing allyl surface-active macromonomer | |
| CN109928879A (en) | A kind of acrylate carbonic ester and its homopolymer and copolymer material | |
| CN113278143A (en) | Efficient unsaturated carbon dioxide-based polyol and preparation method thereof | |
| CN111302960A (en) | Polymerizable surfactant with reducibility and preparation method thereof | |
| CN105367762B (en) | Preparation method of aliphatic polyester | |
| CN115703789B (en) | Seven-membered cyclic carbonate monomer based on D-A reaction and preparation method of polycarbonate | |
| CN101421322B (en) | Method for preparation of 1-alkene-acrylate based copolymer | |
| CN101935395B (en) | Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof | |
| US20220033370A1 (en) | Functionalized a- angelica lactone monomers and polymers obtained therefrom | |
| US20190040191A1 (en) | Recyclable polymers based on ring-fused gamma-butyrolactones | |
| CN109928877A (en) | A kind of styrene carbonic ester and its homopolymer and copolymer material | |
| CN107353414A (en) | Hyperbranched poly caprolactone and preparation method thereof | |
| US20040225081A1 (en) | Oxetane compounds containing cinnamyl functionality | |
| CN105295011B (en) | Preparation method of poly alpha-hydroxy acid | |
| CN105524257B (en) | A kind of full bio-based polyester of ketone group containing and preparation method thereof | |
| CN109694418B (en) | η3-acetoxy method based pi-allyl nickel initiator and method for synthesizing high cis-1,4 content hydroxyl-terminated polybutadiene by using same | |
| US6231783B1 (en) | Replacement solvents for use in chemical synthesis | |
| CN106749807A (en) | A kind of green synthesis method of acrylonitrile polymer | |
| CN109776698A (en) | A kind of amphipathic miscellaneous arm graft polymers and its preparation method and application based on one kettle way |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190625 |