CN104193910A - Method for preparing grafted copolymer through reactive extrusion - Google Patents
Method for preparing grafted copolymer through reactive extrusion Download PDFInfo
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- CN104193910A CN104193910A CN201410422499.5A CN201410422499A CN104193910A CN 104193910 A CN104193910 A CN 104193910A CN 201410422499 A CN201410422499 A CN 201410422499A CN 104193910 A CN104193910 A CN 104193910A
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Abstract
The invention discloses a method for preparing a grafted copolymer through reactive extrusion. The method comprises the following steps of adding a terpolymer of a carbon dioxide-epoxy compound with an unsaturated polyester chain segment, a grafted monomer and an initiating agent which are uniformly mixed into a Haake rheometer at one step to carry out grafting reaction while stirring at the temperature of 65-150 DEG C and the rotating speed of 30-50r/min; after reacting for 10-30min, filtering after soaking the reaction product by using methanol; and carrying out vacuum drying on the solid product to obtain the grafted copolymer. The mass ratio of the terpolymer to the grafted monomer to the initiating agent is 100 to (0.1-50) to (0.01-10); and the grafted monomer is (methyl) acrylate or a vinyl monomer. Both the glass transition temperature and thermal weight loss temperature of the grafted copolymer formed after the monomer is grafted are increased, and the grafted polymer is not dissolved or difficultly dissolved in common organic solvents such as dichloromethane, tetrahydrofuran, ethyl acetate, acetone and the like.
Description
Technical field:
The present invention relates to a kind of adopt reaction to extrude to prepare graft copolymer method, the thermostability of the complete polymkeric substance of grafting, second-order transition temperature and solvent resistance improve.Belong to polymer graft polymerization field.
Background technology:
Epoxy compounds/carbonic acid gas (CO
2) polycarbonate prepared by copolymerization, be that one has biodegradable polymer materials, there is potential application foreground widely in fields such as wrapping material field, bio-medical materials.But because reactive force between polymer chain is smaller, cause the thermotolerance of material, mechanical property not good.Therefore this class epoxy compounds/CO
2there is very large difficulty in the direct application of multipolymer.
In order to improve epoxy compounds/CO
2the performance of multipolymer, can reach the object of application, and investigator has done a large amount of work.At present conventional mode has by adding the 3rd monomer to participate in copolyreaction and carries out chemical modification, the structure that this method can polymer chain, thus regulate and control its performance, but this often can cause polyreaction difficulty; Another one method is carried out modification by melt blending exactly.Melt blending modification is more economy, environmental protection and efficient method of one, both can save step and the expense such as polymkeric substance separation and solvent recuperation in solution reaction process, reduces environmental pollution; Can carry out in as rheometer, forcing machine at ready-made equipment again, production efficiency is high, and therefore people's concern has been received in melt blending modification in recent years.For example, the people such as Pang (J Appl Polym Sci, 2008,107:2854) obtain by poly butylene succinate (PBS) and poly (propylene carbonate) (PPC) simple blend the PPC/PBC matrix material that ductility is good; Compared with PPC, the thermal weight loss temperature of PPC/PBC matrix material has improved 30～60 DEG C.The people such as Fu Luxiang (plastics industry, 2006,34 (11): 14～16) utilize mechanical blending legal system standby completely biological degradation polylactic acid (PLA)/PPC alloy material, PPC adds the good toughness of the system of having given.The people such as Meng (Polym.Eng.Sci., 2007,47:174～180) use ethylene-vinyl alcohol copolymer (EVOH) and PPC simple melt blending at 170 DEG C, find obvious 5% weightless temperature and the maximum heat weight loss rate temperature that has improved PPC that add of EVOH.The people such as Ge (Polym.Eng.Sci., 2004,44:2134～2140) are with unmodified cheap W-Gum and PPC blending and modifying, the matrix material that developed a kind of degradable, have price advantage, mechanical property is good.Above PPC being carried out to modification is all simple and mechanical blend, wherein there is no chemical action.And we extrude by reaction carbonic acid gas and epoxy compounds base co-polymer are carried out to modification, what obtain is graft copolymer, makes like this graft copolymer compared with unmodified multipolymer, its good solubility-resistence, thermotolerance and mechanical property thereof all make moderate progress, and have widened its range of application.Utilize reaction to extrude the modification of carrying out polymkeric substance, simple to operate, aftertreatment is easy, and its development prospect is very wide, has caused people's very big interest.
Summary of the invention
The object of the invention is second-order transition temperature and the thermostability and good solubility-resistence and the mechanical property of improving polymkeric substance of the terpolymer that further improves the carbonic acid gas-epoxy compounds that contains unsaturated polyester segment.The invention provides a kind of efficient graft copolymer and preparation method thereof.The method is carried out graft copolymerization by selecting suitable monomer, reacting under the effect of suitable radical initiator with terpolymer to extrude.Make like this solvent borne of graft copolymer, thermotolerance and mechanical property thereof all make moderate progress, and have widened its range of application.It is simple that this technology has technique, pollutes littlely, is convenient to the advantage of scale operation.
Technical scheme of the present invention is:
A kind of employing reaction is extruded and is prepared graft copolymer method, comprises the following steps:
Under 65～150 DEG C, 30～50r/min rotating speed stir, disposable to terpolymer, grafted monomer and the initiator of the carbonic acid gas-epoxy compounds that contains unsaturated polyester segment mixing joining carried out to graft reaction in Haake torque rheometer, after reaction 10～30min, reaction product after soaking, is filtered methyl alcohol, solid product is dried, obtain the polymkeric substance that grafting is good;
Described material proportion is quality than terpolymer: grafted monomer: initiator=100:0.1～50:0.01～10; Preferred mass ratio is terpolymer: grafted monomer: initiator=10:0.1～5:0.01～0.1.
Described initiator is peroxide radical polymerization initiator or azo radical polymerization initiator.
Described peroxide initiator is: benzoyl peroxide, ditertiary butyl peroxide, isopropyl benzene hydroperoxide, lauroyl peroxide, tert butyl peroxy benzoate, peroxidation titanium dioxide acid (two-2-benzene oxygen ethyl ester), peroxy dicarbonate two (2-diethyl acetamidomalonate), di-isopropyl peroxydicarbonate or methylethyl ketone peroxide.
Described azo-initiator is: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), nitrogen benzide, tert-butyl azodicarboxylate, diethyl azodiformate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide, azo two encircle ethyl formonitrile HCN, azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo di-isopropyl imidazoline salt hydrochlorate or azo dicyano valeric acid.
Described grafted monomer is (methyl) acrylic ester monomer or vinyl monomer.
Described (methyl) acrylic ester monomer is: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) tert-butyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) glycidyl acrylate, BDO two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) esters of acrylic acid (200, 400, 600 etc.), trimethylolpropane tris (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, 1,6-hexylene glycol 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, tetramethylolmethane three (methyl) acrylate, (methyl) Hydroxyethyl acrylate, (methyl) isobornyl acrylate, propoxy-glycerine three (methyl) acrylate, one or more in tetrahydrofurfuryl alcohol (methyl) acrylate and O-phthalic acid diethylene glycol two (methyl) acrylate.
Described vinyl monomer is: one or more in vinylbenzene, p-methylstyrene, Vinylstyrene, NVP, N-caprolactam, vinyl cyanide, vinyl methyl ether, alpha-methyl styrene, vinyl-acetic ester, 2-vinyl pyridine, 4-vinylpridine, N-vinylcarbazole, N-vinyl formamide, N-vinyl acetamide and vinylchlorid.
Beneficial effect of the present invention is: after grafted monomer of the present invention, form graft copolymer second-order transition temperature and thermal weight loss temperature is all improved, second-order transition temperature improves 6～10 DEG C, and thermal weight loss temperature has also improved 15～50 DEG C accordingly.Solvability also can be dissolved in methylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone and other organic solvent by the multipolymer of not grafting, becomes the insoluble or indissoluble after grafting, good solubility-resistence be improved significantly.
Brief description of the drawings
Fig. 1 be in embodiment 1 and 18, PPCNA (terpolymer of carbonic acid gas, propylene oxide and endo-norbornene dicarboxylic anhydride) grafting before and after Dynamic Thermal mechanical paths; Wherein, Fig. 1-a is the Dynamic Thermal mechanical paths figure of PPCNA grafted propylene tert-butyl acrylate (BA), and Fig. 1-b is the Dynamic Thermal mechanical paths figure of PPCNA graft N-vinyl pyrrolidone (NVP).
Fig. 2 be in embodiment 1 and 18, PPCNA grafting before and after thermogravimetric curve; Wherein, Fig. 2-a is weightlessness-thetagram of PPCNA grafting BA, and Fig. 2-b is weight loss rate-thetagram of PPCNA grafting BA; Fig. 2-c is weightlessness-thetagram of PPCNA graft N VP, and Fig. 2-d is weight loss rate-thetagram of PPCNA graft N VP.
Fig. 3 is 1 in example and 18, PPCNA grafted monomer front and back deliquescent comparison diagram in methylene dichloride; Wherein, Fig. 3-a is PPCNA whole dissolving figure in methylene dichloride, Fig. 3-b is that PPCNA connects after NVP insoluble partial graph in methylene dichloride, Fig. 3-c be after PPCNA grafting BA in methylene dichloride insoluble partial graph, Fig. 3-d is the insoluble partial graph that filters out methylene dichloride after PPCNA grafting BA.
Concrete case study on implementation
Below in conjunction with concrete case study on implementation, the present invention is further described, but protection scope of the present invention is not limited only to this.
The terpolymer of the carbonic acid gas-epoxy compounds that contains unsaturated polyester segment the present invention relates to is well known materials, is carbonic acid gas, epoxy compounds and contains the polymkeric substance that two key acid anhydrides copolymerization form.Wherein, epoxy compounds is: propylene oxide, epoxy cyclohexane, epoxy acetone, 1,2-epoxy hexane, epoxy chloropropane, oxyethane, butylene oxide ring, one or more of glycidyl ether; The acid anhydrides that contains two keys is: endo-norbornene dicarboxylic anhydride, exo-norbornene dicarboxylic anhydride, 1,4,5,6,7,7-chlordene-5-norbornylene-2,3-dicarboxylic anhydride, maleic anhydride, dimethyl maleic anhydride, itaconic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, citraconic anhydride, cinnamic anhydride, tetrahydrophthalic anhydride, cis-aconitic anhydride, 2,3-dichloromaleic anhydride, 3,6-oxo bridge-1,2,3,6-Tetra Hydro Phthalic Anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, 4,5-, bis-chloro-phthalic anhydrides, 1-cyclopentenes-1,2-dicarboxylic anhydride, methacrylic anhydride, one or more in isatoic anhydride and phthalic anhydride.The preparation method of raw material of the present invention terpolymer used is shown in Chinese patent (CN102504231A).As the terpolymer PPCNA the present invention relates to is the case study on implementation of the copolymerization of carbonic acid gas and propylene oxide and endo-norbornene dicarboxylic anhydride, see this patent working example 24, be specially:
5mg zinc-cobalt dual-metal cyano complex catalyzer is placed in to 250ml autoclave, at 90 DEG C, take out still 2h left and right with vacuum pump and remove moisture and oxygen micro-in still, be cooled to 25 DEG C of left and right and add 24g propylene oxide and 0.9g endo type norbornene dicarboxylic anhydride, be filled with CO
2and open and stir, kettle is placed in the water-bath that is preheated to 70 DEG C, start reaction, when system temperature arrives and be stabilized in 60 DEG C, control pressure, at 5.5MPa, reacts after 6 hours, and fast cooling is to room temperature, and relief pressure, to normal pressure, obtains foam materials 48.1g.
Other terpolymer with it difference is the difference of epoxy compounds or acid anhydrides, if terpolymer PPCMA is the case study on implementation of the copolymerization of carbonic acid gas, propylene oxide and maleic anhydride, sees this patent working example 22; Terpolymer PPCIA is the copolymerization of carbonic acid gas, propylene oxide and clothing health dicarboxylic anhydride, and its material proportion and reaction conditions are all with this patent working example 24.
Its mechanism is: because acid anhydrides has two keys, have two keys so form on polymer chain, radical initiator can cause two keys and the monomer reaction on acid anhydrides, and then forms graft copolymer.
The invention process case the 1,3～47th, the concrete case study on implementation of grafted monomer in PPCNA multipolymer in Haake torque rheometer; Case study on implementation 2 is concrete case study on implementation of PPCNA multipolymer thing grafted monomer in THF solvent; Case study on implementation 48 is concrete case study on implementation of grafted monomer in PPCMA multipolymer in Haake torque rheometer; Case study on implementation 49 is concrete case study on implementation of grafted monomer in PPCIA multipolymer in Haake torque rheometer;
Case study on implementation 1 is that PPCNA polymkeric substance and monomer tert-butyl acrylate and initiator Diisopropyl azodicarboxylate carry out graft reaction in Haake torque rheometer.
First PPCNA polymkeric substance 50g and grafted monomer tert-butyl acrylate 10g and initiator Diisopropyl azodicarboxylate 0.5g are weighed up, mix; It is 65 DEG C when Haake torque rheometer reaches design temperature, with rotating speed be 30r/min, fast the polymkeric substance mixing and monomer and initiator are added, start to plastify grafting, after reaction 15min, finish, obtain reaction product, methyl alcohol soaks 24 hours, remove unreacted monomer, dry, obtain graftomer.
Fig. 1-a is the Dynamic Thermal mechanical paths figure of PPCNA grafted propylene tert-butyl acrylate (BA), by scheming obviously to find out that glass transformation temperature brings up to 33 DEG C by 27 DEG C.Because obviously improving appears in second-order transition temperature before and after PPCNA grafting, BA monomer is described in the successful grafting of polymer P PCNA.
Fig. 2-a is weightlessness-thetagram of PPCNA grafting BA, and Fig. 2-b is weight loss rate-temperature curve of PPCNA grafting BA; Obviously find out that by Fig. 2-a thermal degradation temperature brings up to 245 DEG C by 230 DEG C, Fig. 2-b can find out that maximum heat degradation temperature brings up to 311 DEG C by 268 DEG C.Due to thermal degradation temperature before and after PPCNA grafting and obviously raising of maximum heat mistake temperature appearance, BA monomer is described in the successful grafting of polymer P PCNA.
Fig. 3 be before and after PPCNA grafted monomer in methylene dichloride deliquescent comparison diagrams, polymkeric substance is added to and in dichloromethane solvent, has carried out 48h immersion.Fig. 3-a is that PPCNA all dissolves in methylene dichloride; Fig. 3-c be after PPCNA grafting BA in methylene dichloride insoluble part, Fig. 3-d be after PPCNA grafting BA in methylene dichloride insoluble part, wherein filtered out the only picture of surplus swelling part of solvent.After conclusion explanation PPCNA grafted monomer has formed crosslinked polymkeric substance, be just insoluble to dichloromethane solvent, before grafting, in dichloromethane solvent, all do not dissolved; So BA monomer in polymer P PCNA success grafting is described.
Case study on implementation 2 is that PPCNA polymkeric substance and monomer tert-butyl acrylate and initiator Diisopropyl azodicarboxylate carry out graft reaction in tetrahydrofuran (THF) (THF).
First PPCNA polymkeric substance 1g and grafted monomer tert-butyl acrylate 0.2g and initiator Diisopropyl azodicarboxylate 0.01g are weighed up; join in there-necked flask; pump drainage three times; under argon shield, add THF20ml; under 75 DEG C of conditions, under reflux, react 5h, reaction finishes rear rotary evaporation and goes out solvent, after methyl alcohol soaks, filters; obtain solid product vacuum-drying under 65 DEG C of conditions good, obtain the polymkeric substance that grafting is good.
Case study on implementation 2 is grafting in solvent, and its aftertreatment complexity, need to remove THF solvent, and the grafting efficiency of graft copolymer is very low, and thermostability and second-order transition temperature do not improve.Degree of crosslinking case study on implementation 1 (grafting in Haake torque rheometer) is 77%, and case study on implementation 2 is 5%; Second-order transition temperature case study on implementation 1 is 33 DEG C, and case study on implementation 2 is 28 DEG C, and grafting PPCNA is not 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 grafting PPCNA is not 230 DEG C; Obviously can find out the better effects if of grafting in Haake torque rheometer.
Case study on implementation 3: grafting embodiment is identical with case study on implementation 1, what just initiator was used is not Diisopropyl azodicarboxylate, 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, what just initiator was used is not Diisopropyl azodicarboxylate, but ditertiary 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, what just initiator was used is not Diisopropyl azodicarboxylate, 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, what just initiator was used is not Diisopropyl azodicarboxylate, 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, what just grafted monomer was used is not tert-butyl acrylate, but isobutyl acrylate.
Case study on implementation 8: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but glycidyl methacrylate.
Case study on implementation 9: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but 1,4 butanediol diacrylate.
Case study on implementation 10: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but polyethyleneglycol diacrylate 600.
Case study on implementation 11: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but Viscoat 295.
Case study on implementation 12: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but Tert-butyl Methacrylate.
Case study on implementation 13: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but Diethylene Glycol dimethacrylate.
Case study on implementation 14: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but polyoxyethylene glycol two (methyl) acrylate 200.
Case study on implementation 15: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but vinylbenzene.
Case study on implementation 16: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but p-methylstyrene.
Case study on implementation 17: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but Vinylstyrene.
Case study on implementation 18: grafting embodiment is identical with case study on implementation 1, what just grafted monomer was used is not tert-butyl acrylate, but NVP.
Fig. 1-b is the Dynamic Thermal mechanical paths figure of PPCNA graft N-vinyl pyrrolidone (NVP), also by scheming obviously to find out that second-order transition temperature brings up to 37 DEG C by 27 DEG C.Because obviously improving appears in second-order transition temperature before and after PPCNA grafting, illustrate that PPCNA graft N VP monomer forms crosslinked polymkeric substance success.
Fig. 2-c is weightlessness-thetagram of PPCNA graft N VP, and Fig. 2-d is weight loss rate-thetagram of PPCNA graft N VP; Also obviously find out that by Fig. 2-c thermal degradation temperature brings up to 272 DEG C by 230 DEG C, Fig. 2-d can find out that maximum heat degradation temperature brings up to 305 DEG C by 268 DEG C.Due to thermal degradation temperature before and after PPCNA grafting and obviously raising of maximum heat mistake temperature appearance, illustrate that PPCNA graft N VP monomer successfully forms crosslinked polymkeric substance.
Fig. 3 be before and after PPCNA grafted monomer in methylene dichloride deliquescent comparison diagrams, polymkeric substance is added to and in dichloromethane solvent, has carried out 48h immersion.Fig. 3-a is that PPCNA all dissolves in methylene dichloride; Fig. 3-b is that PPCNA connects after NVP insoluble part in methylene dichloride.After conclusion explanation PPCNA graft N VP monomer has formed crosslinked polymkeric substance, be just insoluble to dichloromethane solvent, before grafting, in dichloromethane solvent, all do not dissolved; So the success of PPCNA graft N VP monomer is described.
Case study on implementation 19: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but isobutyl acrylate.
Case study on implementation 20: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but glycidyl methacrylate.
Case study on implementation 21: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but 1,4 butanediol diacrylate.
Case study on implementation 22: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but polyethyleneglycol diacrylate 600.
Case study on implementation 23: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but Viscoat 295.
Case study on implementation 24: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but Tert-butyl Methacrylate.
Case study on implementation 25: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but Diethylene Glycol dimethacrylate.
Case study on implementation 26: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but polyoxyethylene glycol two (methyl) acrylate 200.
Case study on implementation 27: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but vinylbenzene.
Case study on implementation 28: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but p-methylstyrene.
Case study on implementation 29: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but Vinylstyrene.
Case study on implementation 30: grafting embodiment is identical with case study on implementation 3, what just grafted monomer was used is not tert-butyl acrylate, but NVP.
Case study on implementation 31: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but isobutyl acrylate.
Case study on implementation 32: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but glycidyl methacrylate.
Case study on implementation 33: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but 1,4 butanediol diacrylate.
Case study on implementation 34: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but polyethyleneglycol diacrylate 600.
Case study on implementation 35: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but Viscoat 295.
Case study on implementation 36: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but Tert-butyl Methacrylate.
Case study on implementation 37: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but Diethylene Glycol dimethacrylate.
Case study on implementation 38: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but polyoxyethylene glycol two (methyl) acrylate 200.
Case study on implementation 39: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but vinylbenzene.
Case study on implementation 40: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but p-methylstyrene.
Case study on implementation 41: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but Vinylstyrene.
Case study on implementation 42: grafting embodiment is identical with case study on implementation 4, what just grafted monomer was used is not tert-butyl acrylate, but NVP.
Case study on implementation 43: grafting embodiment is identical with case study on implementation 18, just material proportion is different, PPCNA polymkeric substance 50g and grafted monomer tert-butyl acrylate 1g and initiator Diisopropyl azodicarboxylate 0.5g.
Case study on implementation 44: grafting embodiment is identical with case study on implementation 18, just material proportion is different, PPCNA polymkeric substance 50g and grafted monomer tert-butyl acrylate 5g and initiator Diisopropyl azodicarboxylate 0.5g.
Case study on implementation 45: grafting embodiment is identical with case study on implementation 18, just material proportion is different, PPCNA polymkeric substance 50g and grafted monomer tert-butyl acrylate 25g and initiator Diisopropyl azodicarboxylate 0.5g.
Case study on implementation 46: grafting embodiment is identical with case study on implementation 18, just material proportion is different, PPCNA polymkeric substance 50g and grafted monomer tert-butyl acrylate 10g and initiator Diisopropyl azodicarboxylate 0.05g.
Case study on implementation 47: grafting embodiment is identical with case study on implementation 18, just material proportion is different, PPCNA polymkeric substance 50g and grafted monomer tert-butyl acrylate 10g and initiator Diisopropyl azodicarboxylate 0.25g.
Case study on implementation 48: grafting embodiment is identical with case study on implementation 18, just the terpolymer of use is not PPCNA, but PPCMA.
Case study on implementation 49: grafting embodiment is identical with case study on implementation 18, just the terpolymer of use is not PPCNA, but PPCIA.
Case study on implementation the 1,3～47th, PPCNA polymkeric substance grafted monomer in Haake torque rheometer; Case study on implementation 2 is PPCNA polymkeric substance grafted monomer in THF solvent; Case study on implementation 48 is PPCMA polymkeric substance grafted monomer in Haake torque rheometer; Case study on implementation 49 is PPCIA polymkeric substance grafted monomer in Haake torque rheometer; The heat decomposition temperature of the graft copolymer after grafting and thermostability are as following table 1
Table 1
After case study on implementation 1～49 grafting, solvability is tested in table 2
Table 2
Note: √-dissolving, ×-insoluble.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. adopt reaction to extrude and prepare a graft copolymer method, it is characterized by the method and comprise the following steps:
65 ~ 150
ounder C, 30 ~ 50r/min rotating speed stir, disposable to terpolymer, grafted monomer and the initiator of the carbonic acid gas-epoxy compounds that contains unsaturated polyester segment mixing joining carried out to graft reaction in Haake torque rheometer, after reaction 10 ~ 30min, reaction product after soaking, is filtered methyl alcohol, solid product vacuum-drying is good, obtain graftomer;
Described material proportion is quality than terpolymer: grafted monomer: initiator=100: 0.1 ~ 50: 0.01 ~ 10;
Described initiator is peroxide radical polymerization initiator or azo radical polymerization initiator;
Described grafted monomer is (methyl) acrylic ester monomer or vinyl monomer.
2. employing reaction as claimed in claim 1 is extruded and is prepared graft copolymer method, it is characterized by described peroxide initiator and is: benzoyl peroxide, ditertiary butyl peroxide, isopropyl benzene hydroperoxide, lauroyl peroxide, tert butyl peroxy benzoate, peroxidation titanium dioxide acid (two-2-benzene oxygen ethyl ester), peroxy dicarbonate two (2-diethyl acetamidomalonate), di-isopropyl peroxydicarbonate or methylethyl ketone peroxide.
3. employing reaction as claimed in claim 1 is extruded and is prepared graft copolymer method, it is characterized by described azo-initiator and is: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), nitrogen benzide, tert-butyl azodicarboxylate, diethyl azodiformate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide, azo two encircle ethyl formonitrile HCN, azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo di-isopropyl imidazoline salt hydrochlorate or azo dicyano valeric acid.
4. employing reaction as claimed in claim 1 is extruded and is prepared graft copolymer method, it is characterized by described (methyl) acrylic ester monomer and is: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) tert-butyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) glycidyl acrylate, BDO two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) esters of acrylic acid (200, 400, 600 etc.), trimethylolpropane tris (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, 1,6-hexylene glycol 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, tetramethylolmethane three (methyl) acrylate, (methyl) Hydroxyethyl acrylate, (methyl) isobornyl acrylate, propoxy-glycerine three (methyl) acrylate, one or more in tetrahydrofurfuryl alcohol (methyl) acrylate and O-phthalic acid diethylene glycol two (methyl) acrylate.
5. employing reaction as claimed in claim 1 is extruded and is prepared graft copolymer method, it is characterized by described vinyl monomer and is: one or more in vinylbenzene, p-methylstyrene, Vinylstyrene, NVP, N-caprolactam, vinyl cyanide, vinyl methyl ether, alpha-methyl styrene, vinyl-acetic ester, 2-vinyl pyridine, 4-vinylpridine, N-vinylcarbazole, N-vinyl formamide, N-vinyl acetamide and vinylchlorid.
6. employing reaction as claimed in claim 1 is extruded and is prepared graft copolymer method, and it is characterized by the preferred mass ratio of material proportion is terpolymer: grafted monomer: initiator=10: 0.1 ~ 5: 0.01 ~ 0.1.
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| CN113943405A (en) * | 2021-05-08 | 2022-01-18 | 天津科技大学 | Crease self-repairing polylactic acid film |
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