CN104193910B - A kind of employing reactive extrursion prepares graft copolymer method - Google Patents
A kind of employing reactive extrursion prepares graft copolymer method Download PDFInfo
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Abstract
The present invention uses reactive extrursion to prepare graft copolymer method for one, and the method comprises the following steps: 65 ~ 150oUnder the stirring of C, 30 ~ 50r/min rotating speed, graft reaction is carried out in the terpolymer of carbon dioxide epoxide, grafted monomers and the initiator containing unsaturated polyester (UP) segment of mix homogeneously are disposably joined Haake torque rheometer, after reaction 10 ~ 30min, product is filtered after methanol soaks, solid product is vacuum dried, obtains the polymer being grafted；Wherein, material proportion be quality than terpolymer: grafted monomers: initiator=100:0.1 ~ 50:0.01 ~ 10；Described grafted monomers is (methyl) esters of acrylic acid or vinyl monomer.Forming graft copolymer glass transition temperature after grafted monomers of the present invention and thermal weight loss temperature all increases, the polymer after grafting common are insoluble in machine solvent or indissoluble at dichloromethane, oxolane, ethyl acetate, acetone etc..
Description
Technical field:
The present invention relates to a kind of use reactive extrursion to prepare graft copolymer method, the polymer being grafted thermally-stabilised
Property, glass transition temperature and solvent resistance are improved.Belong to polymer glycerol polymerization field.
Background technology:
Epoxide/carbon dioxide (CO2) Merlon prepared by copolymerization, it is that one has biodegradable polymerization
Thing material, has potential application foreground widely in fields such as packaging material field, bio-medical materials.Yet with polymer
Inter-chain action power is smaller, causes the thermostability of material, mechanical property the best.The most this kind of epoxide/CO2Copolymer
Directly there is the biggest difficulty in application.
In order to improve epoxide/CO2The performance of copolymer, it is possible to reaching the purpose of application, researcher has done in a large number
Work.At present conventional mode has and participates in copolyreaction and carry out chemical modification by adding Third monomer, and this method can
With the structure of polymer chain, thus regulate and control its performance, but this often can cause polyreaction difficulty；Another one method is led to exactly
Cross melt blending to be modified.Melt blending modification is one more economy, environmental protection and efficient method, both can save solution anti-
During Ying, step and the expense such as polymer separation and solvent recovery, reduces environmental pollution；Again can be in ready-made equipment such as rheology
Carrying out in instrument, extruder, production efficiency is high, and melt blending modification the most in recent years have received the concern of people.Such as, Pang etc.
People (J Appl Polym Sci, 2008,107:2854) uses poly butylene succinate (PBS) and poly (propylene carbonate) (PPC)
Simple blend obtains the PPC/PBC composite that ductility is good；Compared with PPC, the thermal weight loss temperature of PPC/PBC composite carries
High 30～60 DEG C.Fu Luxiang et al. (plastics industry, 2006,34 (11): 14～16) utilizes mechanical blending method to be prepared for completely
Biodegradable polylactic acid (PLA)/PPC alloy material, the addition of PPC imparts the good toughness of system.Meng et al.
(Polym.Eng.Sci., 2007,47:174～180) use ethylene-vinyl alcohol copolymer (EVOH) and PPC simple at 170 DEG C
Melt blending, finds that the addition of EVOH significantly improves 5% weightless temperature and the maximum heat weight loss rate temperature of PPC.Ge et al.
(Polym.Eng.Sci., 2004,44:2134～2140), with unmodified cheap corn starch and PPC blending and modifying, develop
A kind of degradable, there is price advantage, composite that mechanical property is good.It is all simple and mechanical common for being modified PPC above
Mixed, without chemical action.And carbon dioxide and epoxide base co-polymer are modified by we by reactive extrursion,
Obtain is graft copolymer, so prepare graft copolymer compared with unmodified copolymer, its solvent resistance, thermostability and
Its mechanical property all makes moderate progress, and has widened its range of application.Reactive extrursion is utilized to carry out the modification of polymer, simple to operate,
Post processing is easy, and its development prospect is the most wide, causes the great interest of people.
Summary of the invention
It is an object of the invention to improve further the ternary of the carbon dioxide-epoxide containing unsaturated polyester (UP) segment
The glass transition temperature of copolymer and heat stability and improve solvent resistance and the mechanical property of polymer.The invention provides
A kind of efficiently graft copolymer and preparation method thereof.The method is by selecting suitable monomer, at suitable radical initiator
Effect under in reactive extrursion, carry out graft copolymerization with terpolymer.So prepare the solvent borne of graft copolymer,
Thermostability and mechanical property thereof all make moderate progress, and have widened its range of application.It is simple that this technology has technique, pollutes little, it is simple to
The advantage of large-scale production.
The technical scheme is that
A kind of employing reactive extrursion prepares graft copolymer method, comprises the following steps:
65～150 DEG C, 30～50r/min rotating speed stirring under, by mix homogeneously containing the two of unsaturated polyester (UP) segment
The terpolymer of carbonoxide-epoxide, grafted monomers and initiator connect in disposably joining Haake torque rheometer
Branch reaction, after reaction 10～30min, filters product after methanol soaks, and solid product is dried, obtains being grafted
Polymer；
Described material proportion be quality than terpolymer: grafted monomers: initiator=100:0.1～50:0.01～
10；Preferably mass ratio is terpolymer: grafted monomers: initiator=10:0.1～5:0.01～0.1.
Described initiator is peroxide radical polymerization initiator or azo type free radical polymerization initiator.
Described peroxide type initiators is: benzoyl peroxide, di-tert-butyl peroxide, isopropyl benzene hydroperoxide,
Lauroyl peroxide, tert butyl peroxy benzoate, peroxidating titanium dioxide acid (double-2-benzene oxygen ethyl ester), peroxidating two carbon
Acid two (2-diethyl acetamidomalonates), di-isopropyl peroxydicarbonate or methyl ethyl ketone peroxide.
Described azo-initiator is: azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), diphenyl diimide, the tertiary fourth of azoformic acid two
Ester, diethyl azodiformate, AMBN, azo isobutyl cyano group Methanamide, azo bicyclo-ethyl formonitrile HCN, azo two are different
Butanoic acid dimethyl ester, azo-bis-isobutyrate hydrochloride, azo diisopropyl imidazoline hydrochloride or azo dicyano valeric acid.
Described grafted monomers is (methyl) acrylic ester monomer or vinyl monomer.
Described (methyl) acrylic ester monomer is: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl)
Tert-butyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) glycidyl acrylate, 1,
4-butanediol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Polyethylene Glycol two (methyl) esters of acrylic acid
(200,400,600 etc.), trimethylolpropane tris (methyl) acrylate, two trimethylolpropane four (methyl) acrylate,
Dipentaerythrite five (methyl) acrylate, 1,6-HD two (methyl) acrylate, tripropylene glycol two (methyl) propylene
Acid esters, dipropylene glycol two (methyl) acrylate, (methyl) dodecyl acrylate, (methyl) Isooctyl acrylate monomer, ethylene glycol bisthioglycolate
(methyl) acrylate, tetramethylolmethane three (methyl) acrylate, (methyl) 2-(Acryloyloxy)ethanol, (methyl) isobomyl acrylate
Ester, propoxylated glycerol three (methyl) acrylate, tetrahydrofurfuryl alcohol (methyl) acrylate and O-phthalic acid diethylene glycol two (first
Base) one or more in acrylate.
Described vinyl monomer is: styrene, p-methylstyrene, divinylbenzene, NVP,
N-caprolactam, acrylonitrile, vinyl methyl ether, α-methyl styrene, vinyl acetate, 2-vinylpyridine, 4-
One or more in vinylpyridine, N-VCz, N-vinyl formamide, N-vinyl acetamide and vinyl chloride.
Form graft copolymer glass transition temperature after the invention have the benefit that grafted monomers of the present invention and heat is lost
Degree of reviewing all is improved, and glass transition temperature improves 6～10 DEG C, and thermal weight loss temperature has also been correspondingly improved 15～50 DEG C.Molten
Solution property also can be dissolved in dichloromethane, oxolane, ethyl acetate, acetone and other organic solvent by non-grafted copolymer, becomes
Insoluble or indissoluble after grafting, solvent resistance be improved significantly.
Accompanying drawing explanation
Fig. 1 is in embodiment 1 and 18, PPCNA (carbon dioxide, expoxy propane and the ternary of endo-carbic anhydride
Copolymer) grafting before and after dynamic thermomechanical curve；Wherein, Fig. 1-a is the Dynamic Thermal of PPCNA grafted propylene tert-butyl acrylate (BA)
Mechanical paths figure, Fig. 1-b is the dynamic thermomechanical curve chart of PPCNA graft N-vinyl pyrrolidone (NVP).
Fig. 2 is in embodiment 1 and 18, the thermogravimetric curve before and after PPCNA grafting；Wherein, Fig. 2-a is that PPCNA is grafted BA
Weightlessness-temperature profile, Fig. 2-b be PPCNA grafting BA weight loss rate-temperature profile；Fig. 2-c is PPCNA graft N VP
Weightlessness-temperature profile, Fig. 2-d is the weight loss rate-temperature profile of PPCNA graft N VP.
Fig. 3 is 1 in example and 18, before and after PPCNA grafted monomers in dichloromethane deliquescent comparison diagram；Wherein,
Fig. 3-a is PPCNA whole dissolving figures in dichloromethane, and Fig. 3-b is that PPCNA connects after NVP insoluble part figure in dichloromethane,
Fig. 3-c be PPCNA grafting BA after in dichloromethane insoluble part figure, Fig. 3-d be PPCNA grafting BA after filter out dichloromethane
Insoluble part figure.
It is embodied as case
Below in conjunction with being embodied as case, the present invention is further described, but protection scope of the present invention is not limited only to this.
The terpolymer of the carbon dioxide-epoxide containing unsaturated polyester (UP) segment that the present invention relates to is known
Material, is carbon dioxide, epoxide and the polymer formed containing double bond anhydride copolymers.Wherein, epoxide is: ring
Ethylene Oxide, 7-oxa-bicyclo[4.1.0, epoxy acetone, 1,2-oxepane, epoxychloropropane, oxirane, epoxy butane, (+)-2,3-Epoxy-1-propanol
One or more of ether；Anhydride containing double bond is: endo-carbic anhydride, exo-carbic anhydride, Isosorbide-5-Nitrae,
5,6,7,7-chlordene-5-norborene-2,3-dicarboxylic anhydride, maleic anhydride, dimethyl maleic anhydride, itaconic anhydride, chlorendic anhydride,
Citraconic anhydride, cinnamic anhydride, THPA, cis-aconitic anhydride, 2,3-dichloromaleic anhydrides, 3,6-oxygen bridge-1,2,3,6-tetra-
Hydrogen phthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, 4,5-bis-chloro-phthalic anhydrides, 1-cyclopentenes-1,2-dicarboxylic anhydride, methyl
One or more in acrylic anhydride, isatoic anhydride and phthalic anhydride.The preparation method of the terpolymer used by raw material of the present invention is shown in
Chinese patent (CN102504231A).Such as the terpolymer PPCNA i.e. carbon dioxide that the present invention relates to and expoxy propane and
The case study on implementation of the copolymerization of endo-carbic anhydride, is shown in this patent Example 24, particularly as follows:
5mg zinc-cobalt dual-metal cyano complex catalyst is placed in 250ml autoclave, at 90 DEG C, uses vacuum pump
Take out still about 2h and remove moisture and the oxygen of trace in still, be cooled to about 25 DEG C and add 24g expoxy propane and 0.9g endo type
Carbic anhydride, is filled with CO2And open stirring, kettle is placed in the water-bath being pre-heated to 70 DEG C, starts reaction, be
System temperature arrives and stablizes when 60 DEG C, and control pressure is at 5.5MPa, after reacting 6 hours, and fast cooling to room temperature, discharge pressure
To normal pressure, obtain foamed materials 48.1g.
The different part of other terpolymer is the difference of epoxide or anhydride, such as terpolymer
The case study on implementation of the copolymerization of PPCMA i.e. carbon dioxide, expoxy propane and maleic anhydride, is shown in this patent Example 22；Ternary polymerization
Thing PPCIA i.e. carbon dioxide, expoxy propane and the copolymerization of clothing health dicarboxylic anhydride, its material proportion and reaction condition are all real with this patent
Execute example 24.
Its mechanism is: owing to anhydride has double bond, has double bond so being formed on polymer chain, and radical initiator can draw
Turn sour the double bond on acid anhydride and monomer reaction, and then forms graft copolymer.
Case study on implementation 1,3～47 of the present invention is being embodied as of grafted monomers in PPCNA copolymer in Haake torque rheometer
Case；Case study on implementation 2 be PPCNA copolymer thing in THF solvent grafted monomers be embodied as case；Case study on implementation 48 be
In Haake torque rheometer in PPCMA copolymer grafted monomers be embodied as case；Case study on implementation 49 is in Haake torque rheometer
In PPCIA copolymer, grafted monomers is embodied as case；
Case study on implementation 1 is that PPCNA polymer and monomer propylene tert-butyl acrylate and initiator azodiisobutyronitrile are at Haake stream
Graft reaction is carried out in becoming instrument.
First by PPCNA polymer 50g and grafted monomers tert-butyl acrylate 10g and initiator azodiisobutyronitrile 0.5g
Weigh up, mix homogeneously；It is 65 DEG C when Haake torque rheometer reaches design temperature, and rotating speed is 30r/min, quickly poly-mix
Compound and monomer and initiator add, and proceed by plasticizing grafting, terminate, obtain product after reaction 15min, and methanol soaks
24 hours, remove unreacted monomer, be dried, obtain graft polymers.
Fig. 1-a is the dynamic thermomechanical curve chart of PPCNA grafted propylene tert-butyl acrylate (BA), figure will become apparent from glass and turn
Temperature is brought up to 33 DEG C by 27 DEG C.Before and after being grafted due to PPCNA, significantly improving occurs in glass transition temperature, and polymer is described
PPCNA has successfully been grafted BA monomer.
Fig. 2-a is the weightlessness-temperature profile of PPCNA grafting BA, and Fig. 2-b is the weight loss rate-temperature of PPCNA grafting BA
Curve；Be will become apparent from thermal degradation temperature by Fig. 2-a and brought up to 245 DEG C by 230 DEG C, Fig. 2-b can be seen that maximum heat degradation temperature
311 DEG C are brought up to by 268 DEG C.Before and after being grafted due to PPCNA, significantly improving occur in thermal degradation temperature and maximum heat mistake temperature, explanation
Polymer P PCNA has successfully been grafted BA monomer.
Fig. 3 be before and after PPCNA grafted monomers in dichloromethane deliquescent comparison diagram, it is molten that polymer is added to dichloromethane
Agent has carried out 48h immersion.Fig. 3-a is that PPCNA all dissolves in dichloromethane；Fig. 3-c be PPCNA grafting BA after at dichloro
Insoluble part in methane, Fig. 3-d be after PPCNA grafting BA in dichloromethane insoluble part, filtered out solvent only
The picture of surplus swollen part.Conclusion explanation PPCNA grafted monomers is just molten insoluble in dichloromethane after defining the polymer of crosslinking
Agent, non-grafted before all dissolve in dichloromethane solvent；So explanation polymer P PCNA is successfully grafted BA monomer.
Case study on implementation 2 is that PPCNA polymer and monomer propylene tert-butyl acrylate and initiator azodiisobutyronitrile are at tetrahydrochysene furan
Mutter and (THF) carries out graft reaction.
First by PPCNA polymer 1g and grafted monomers tert-butyl acrylate 0.2g and initiator azodiisobutyronitrile
0.01g weighs up, and joins in there-necked flask, pump drainage three times, adds THF20ml, be heated to reflux under the conditions of 75 DEG C under argon shield
Under carry out reacting 5h, reaction terminates rear rotary evaporation and goes out solvent, and methanol filters after soaking, and obtains solid product true under the conditions of 65 DEG C
Empty dried, obtain the polymer being grafted.
Case study on implementation 2 is to be grafted in a solvent, and its post processing is complicated, needs to remove THF solvent, and graft copolymer
Grafting efficiency is the lowest, and heat stability and glass transition temperature do not improve.Degree of cross linking case study on implementation 1 is (at Haake torque rheometer
Interior grafting) it is 77%, case study on implementation 2 is 5%；Glass transition temperature case study on implementation 1 is 33 DEG C, and case study on implementation 2 is 28 DEG C, and
Non-grafted PPCNA is 27 DEG C；Heat decomposition temperature case study on implementation 1 is 248 DEG C, and case study on implementation 2 is 233 DEG C, and non-grafted PPCNA is
230℃；Substantially can be seen that the effect of grafting is more preferable in Haake torque rheometer.
Case study on implementation 3: grafting embodiment is identical with case study on implementation 1, and simply initiator is not azodiisobutyronitrile,
But 2,2'-Azobis(2,4-dimethylvaleronitrile).Design temperature is 50 DEG C, and rotating speed is 30r/min.
Case study on implementation 4: grafting embodiment is identical with case study on implementation 1, and simply initiator is not azodiisobutyronitrile,
But di-tert-butyl peroxide.Design temperature is 125 DEG C, and rotating speed is 30r/min.
Case study on implementation 5: grafting embodiment is identical with case study on implementation 1, and simply initiator is not azodiisobutyronitrile,
But isopropyl benzene hydroperoxide.Design temperature is 115 DEG C, and rotating speed is 30r/min.
Case study on implementation 6: grafting embodiment is identical with case study on implementation 1, and simply initiator is not azodiisobutyronitrile,
But benzoyl peroxide.Design temperature is 75 DEG C, and rotating speed is 30r/min.
Case study on implementation 7: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Isobutyl 2-propenoate.
Case study on implementation 8: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but glycidyl methacrylate.
Case study on implementation 9: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but BDO diacrylate.
Case study on implementation 10: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but polyethyleneglycol diacrylate 600.
Case study on implementation 11: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but trimethylolpropane trimethacrylate.
Case study on implementation 12: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Tert-butyl Methacrylate.
Case study on implementation 13: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but dimethacrylate.
Case study on implementation 14: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Polyethylene Glycol two (methyl) acrylate 200.
Case study on implementation 15: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but styrene.
Case study on implementation 16: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but p-methylstyrene.
Case study on implementation 17: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but divinylbenzene.
Case study on implementation 18: grafting embodiment is identical with case study on implementation 1, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but NVP.
Fig. 1-b is the dynamic thermomechanical curve chart of PPCNA graft N-vinyl pyrrolidone (NVP), also substantially sees by scheming
Go out glass transition temperature and brought up to 37 DEG C by 27 DEG C.Before and after being grafted due to PPCNA, significantly improving occurs in glass transition temperature,
Illustrate that PPCNA graft N VP monomer forms the polymer success of crosslinking.
Fig. 2-c is the weightlessness-temperature profile of PPCNA graft N VP, and Fig. 2-d is the weight loss rate-temperature of PPCNA graft N VP
Write music line chart；Also be will become apparent from thermal degradation temperature by Fig. 2-c and brought up to 272 DEG C by 230 DEG C, Fig. 2-d can be seen that maximum heat drop
Solve temperature and brought up to 305 DEG C by 268 DEG C.Before and after being grafted due to PPCNA, substantially carrying occur in thermal degradation temperature and maximum heat mistake temperature
Height, illustrates that PPCNA graft N VP monomer is successfully formed the polymer of crosslinking.
Fig. 3 be before and after PPCNA grafted monomers in dichloromethane deliquescent comparison diagram, it is molten that polymer is added to dichloromethane
Agent has carried out 48h immersion.Fig. 3-a is that PPCNA all dissolves in dichloromethane；Fig. 3-b is that PPCNA connects after NVP at dichloro
Insoluble part in methane.Conclusion explanation PPCNA graft N VP monomer is just molten insoluble in dichloromethane after defining the polymer of crosslinking
Agent, non-grafted before all dissolve in dichloromethane solvent；So explanation PPCNA graft N VP monomer success.
Case study on implementation 19: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Isobutyl 2-propenoate.
Case study on implementation 20: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but glycidyl methacrylate.
Case study on implementation 21: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but BDO diacrylate.
Case study on implementation 22: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but polyethyleneglycol diacrylate 600.
Case study on implementation 23: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but trimethylolpropane trimethacrylate.
Case study on implementation 24: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Tert-butyl Methacrylate.
Case study on implementation 25: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but dimethacrylate.
Case study on implementation 26: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Polyethylene Glycol two (methyl) acrylate 200.
Case study on implementation 27: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but styrene.
Case study on implementation 28: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but p-methylstyrene.
Case study on implementation 29: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but divinylbenzene.
Case study on implementation 30: grafting embodiment is identical with case study on implementation 3, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but NVP.
Case study on implementation 31: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Isobutyl 2-propenoate.
Case study on implementation 32: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but glycidyl methacrylate.
Case study on implementation 33: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but BDO diacrylate.
Case study on implementation 34: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but polyethyleneglycol diacrylate 600.
Case study on implementation 35: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but trimethylolpropane trimethacrylate.
Case study on implementation 36: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Tert-butyl Methacrylate.
Case study on implementation 37: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but dimethacrylate.
Case study on implementation 38: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but Polyethylene Glycol two (methyl) acrylate 200.
Case study on implementation 39: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but styrene.
Case study on implementation 40: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but p-methylstyrene.
Case study on implementation 41: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but divinylbenzene.
Case study on implementation 42: grafting embodiment is identical with case study on implementation 4, and simply grafted monomers is not the tertiary fourth of acrylic acid
Ester, but NVP.
Case study on implementation 43: grafting embodiment is identical with case study on implementation 18, and simply material proportion is different, PPCNA is polymerized
Thing 50g and grafted monomers tert-butyl acrylate 1g and initiator azodiisobutyronitrile 0.5g.
Case study on implementation 44: grafting embodiment is identical with case study on implementation 18, and simply material proportion is different, PPCNA is polymerized
Thing 50g and grafted monomers tert-butyl acrylate 5g and initiator azodiisobutyronitrile 0.5g.
Case study on implementation 45: grafting embodiment is identical with case study on implementation 18, and simply material proportion is different, PPCNA is polymerized
Thing 50g and grafted monomers tert-butyl acrylate 25g and initiator azodiisobutyronitrile 0.5g.
Case study on implementation 46: grafting embodiment is identical with case study on implementation 18, and simply material proportion is different, PPCNA is polymerized
Thing 50g and grafted monomers tert-butyl acrylate 10g and initiator azodiisobutyronitrile 0.05g.
Case study on implementation 47: grafting embodiment is identical with case study on implementation 18, and simply material proportion is different, PPCNA is polymerized
Thing 50g and grafted monomers tert-butyl acrylate 10g and initiator azodiisobutyronitrile 0.25g.
Case study on implementation 48: grafting embodiment is identical with case study on implementation 18, and terpolymer simply is not PPCNA,
But PPCMA.
Case study on implementation 49: grafting embodiment is identical with case study on implementation 18, and terpolymer simply is not PPCNA,
But PPCIA.
Case study on implementation 1,3～47 is PPCNA polymer grafted monomers in Haake torque rheometer；Case study on implementation 2 is that PPCNA gathers
Compound is grafted monomers in THF solvent；Case study on implementation 48 is PPCMA polymer grafted monomers in Haake torque rheometer；Enforcement case
Example 49 is PPCIA polymer grafted monomers in Haake torque rheometer；Heat decomposition temperature and the heat of the graft copolymer after grafting are steady
Qualitative such as table 1 below
Table 1
After case study on implementation 1～49 grafting, dissolubility test is shown in Table 2
Table 2
Note: √-dissolving, ×-insoluble.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. use reactive extrursion to prepare a graft copolymer method, it is characterized by that the method comprises the following steps:
65 ~ 150oC, 30 ~ 50r/min rotating speed stirring under, by the carbon dioxide containing unsaturated polyester (UP) segment of mix homogeneously-
The terpolymer of epoxide, grafted monomers and initiator carry out graft reaction in disposably joining Haake torque rheometer,
After reaction 10 ~ 30min, product is filtered after methanol soaks, solid product is vacuum dried, obtains glycerol polymerization
Thing；
Described material proportion be quality than terpolymer: grafted monomers: initiator=100: 0.1 ~ 50: 0.01 ~ 10；
Described initiator is peroxide radical polymerization initiator or azo type free radical polymerization initiator；
Described grafted monomers is (methyl) acrylic ester monomer or vinyl monomer；
Described (methyl) acrylic ester monomer is: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propylene
Tert-butyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) glycidyl acrylate, 1,4-fourth
Glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Polyethylene Glycol two (methyl) esters of acrylic acid, three hydroxyls
Methylpropane three (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, dipentaerythrite five (methyl)
Acrylate, 1,6-HD two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl)
Acrylate, (methyl) dodecyl acrylate, (methyl) Isooctyl acrylate monomer, ethylene glycol bisthioglycolate (methyl) acrylate, Ji Wusi
Alcohol three (methyl) acrylate, (methyl) 2-(Acryloyloxy)ethanol, (methyl) isobornyl acrylate, propoxylated glycerol three (methyl)
One in acrylate, tetrahydrofurfuryl alcohol (methyl) acrylate and O-phthalic acid diethylene glycol two (methyl) acrylate or
Several；
Described vinyl monomer is: styrene, p-methylstyrene, divinylbenzene, NVP, N-second
Thiazolinyl caprolactam, acrylonitrile, vinyl methyl ether, α-methyl styrene, vinyl acetate, 2-vinylpyridine, 4-ethylene
One or more in yl pyridines, N-VCz, N-vinyl formamide, N-vinyl acetamide and vinyl chloride.
2. employing reactive extrursion as claimed in claim 1 prepares graft copolymer method, it is characterized by described peroxide
Class initiator is: benzoyl peroxide, di-tert-butyl peroxide, isopropyl benzene hydroperoxide, lauroyl peroxide, tert-butyl group mistake
Oxybenzene formic acid esters, peroxidating titanium dioxide acid (double-2-benzene oxygen ethyl ester), peroxy dicarbonate two (2-diethyl acetamidomalonate), peroxide
Change two diisopropyl carbonate or methyl ethyl ketone peroxide.
3. employing reactive extrursion as claimed in claim 1 prepares graft copolymer method, it is characterized by that described azo draws
Send out agent be: azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), diphenyl diimide, tert-butyl azodicarboxylate, diethyl azodiformate,
AMBN, azo isobutyl cyano group Methanamide, azo bicyclo-ethyl formonitrile HCN, azo-bis-iso-dimethyl, azo two are different
Butanimidamide, monohydrochloride, azo diisopropyl imidazoline hydrochloride or azo dicyano valeric acid.
4. employing reactive extrursion as claimed in claim 1 prepares graft copolymer method, it is characterized by that quality of material ratio is three
Membered copolymer: grafted monomers: initiator=10: 0.1 ~ 5: 0.01 ~ 0.1.
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