CN101450982A - Couple method of polyolefin molecular chain - Google Patents
Couple method of polyolefin molecular chain Download PDFInfo
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Abstract
The invention relates to a method for coupling polyolefin molecular chains. The method comprises the following steps: through solution grafting reaction or melt grafting reaction, 0 to 15 weight portions of vinyl monomers containing polyfunctional groups and 100 weight portions of polyolefin are subjected to grafting reaction at a certain temperature under the action of 0.02 to 10.0 weight portions of initiator and the synergism of 0 to 15 weight portions of second olefin monomers, so as to prepare grafted polyolefin of which a side chain has functional groups, and 100 weight portions of grafted polyolefin is added with 0.1 to 20 weight portions of polyfunctional-group organic coupling agent and 0 to 10.0 weight portions of antioxidant at a certain temperature through solution reaction or melt blending reaction, so as to couple the grafted polyolefin. Compared with the prior art, the method can produce high-strength long-shoot polyolefin, and has the advantages of controllable coupling degree, low cost and high productivity.
Description
Technical field
The invention belongs to polymer polymerizing, processing and functionalization technical field, relate to a kind of coupling method of molecular polyolefin chain.
Background technology
With polypropylene, polyethylene is that the polyolefine of representative is one of thermoplastic macromolecule material that is most widely used.But,, descend rapidly above its melt strength behind the fusing point, thereby cause the shortcoming that its melt strength is low and be difficult to blowing and foaming because the softening point of hemicrystalline polypropylene is very approaching with fusing point.And shortcomings such as polyethylene is lower because of its fusing point, physical strength is not high, environmental stress resistance poor-performing have limited poly range of application.Can reduce polyacrylic percent thermal shrinkage by the coupling modification, improve polyacrylic shock strength, enlarge the scope of its application.It is to improve the Perfected process of polyethylene weak point that polyethylene is carried out coupling processing, through coupling, the three-dimensional network that forms can be improved performances such as poly thermal distortion, wearing and tearing, viscous yielding, chemical resistant properties, stress cracking resistance greatly, poly impact and tensile strength are improved, shrinking percentage reduces, deficiencies such as use temperature is low improve, and the coupling product also has shape memory function.
The polyolefine coupling method mainly contains three kinds: peroxide crosslinking, cross-linking radiation and crosslinked with silicane.Irradiation crosslinking is subjected to thickness limits, has shortcomings such as cost height, source of radiation be limited; The peroxide crosslinking method exists the cladodification rate low, and easily degraded or excessively crosslinked such as is difficult to stablize at defective, and silane cross-linking method exists and need use water as cross-linking catalyst, can only be crosslinked again after finishing goods, and in fact except that making tubing, lack other industrial production and be worth.As seen above three kinds of methods commonly used can not satisfy polyolefinic long shootizationization and industrial applications.
With Chinese patent CN1380344 is example, it has introduced a kind of mechanochemical method of polyolefin plastics fusion-grafting vinyl monomer, vinyl monomer, lubricant and polyolefine are mixed the back adding to be had in the forcing machine of ultrasonic generator and ultrasonic transducer, carry out continuous extruding graft reaction, obtain polyolefin graft polymers or multipolymer.But the equipment more complicated that this patent is used on the one hand, the polyolefine of Shi Yonging must be polyethylene or contain ethene segmental multipolymer in addition, thereby has limited the application aspect polypropylene, and percentage of grafting is lower.Japanese Patent JP6172459 has introduced in the presence of the special common monomer of a class, carries out the technology of graft-modified polyolefin by vinyl monomer and superoxide, can prevent to degrade and crosslinked in improve the percentage of grafting of vinyl monomer and be used for extrusion molding.Though this patent has suppressed polyolefinic degraded and crosslinked, the percentage of grafting of vinyl monomer still can not obtain enough raisings.And this type of domestic patent mostly is to adopt cost height, the uppity radiation grafted method of percentage of grafting, and for example Chinese patent CN1485354 and CN1482151 adopt radiation grafted method to obtain functional polyolefin resin.
The coupling polyolefine that uses at aspects such as insulated cable, foam material and thermoplastic elastomers mostly is to use peroxide crosslinking, cross-linking radiation and crosslinked with silicane to prepare both at home and abroad.The work-ing life of having reduced the size of inner spherocrystal and having improved cable as the insulated cable of Chinese patent CN1300085 by the crosslinked preparation of oxide compound; Japanese Patent JP9104052 has prepared by radiation crosslinking does not have the drinking-water of peculiar smell bottle; Chinese patent CN1438262 has introduced a kind of silane crosslinking polyolefin elastic body composition.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of high-intensity long shootization polyolefine of can producing for the weak point that overcomes above-mentioned prior art existence, and the coupling degree is controlled, and is with low cost, the coupling method of the molecular polyolefin chain that productivity is high.
Purpose of the present invention can be achieved through the following technical solutions: a kind of coupling method of molecular polyolefin chain, it is characterized in that, this method is by solution graft copolymerization reaction or melting graft reaction, under 0.02～10.0 weight part action of evocating, make 0～15 weight part contain multi-functional vinyl monomer and carry out graft reaction at a certain temperature with 100 weight part polyolefine under 0～15 weight part, second olefinic monomer synergy, the preparation side chain has the graft polyolefin of functional group; Get the graft polyolefin of 100 weight parts,, add the polyfunctional group organic coupling agent of 0.1～20 weight part and the oxidation inhibitor of 0～10.0 weight part at a certain temperature described graft polyolefin is carried out coupling by solution reaction or melt blending reaction.
Described polyolefine comprises the multipolymer of general purpose polypropylene, general polyethylene or ethylene, propylene, and its melt flow rate (MFR) is 0.1g/10min～50g/10min; Describedly contain multi-functional vinyl monomer and comprise in vinylformic acid, maleic anhydride, methacrylic acid, fumaric acid, methylene-succinic acid, undecylenic acid, glycidyl methacrylate, acrylamide, N hydroxymethyl acrylamide, Hydroxyethyl acrylate, the Propylene glycol monoacrylate one or several; Described second olefinic monomer comprises one or more in vinylbenzene, Vinylstyrene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, butyl acrylate, the butyl methacrylate; Described initiator comprises dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, tert butyl peroxy benzoate, 1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 4-, perhaps one or several in azobisisobutyronitrile, azo two eyeball in different heptan.
Described solution grafting comprises the steps: second olefinic monomer that contains multi-functional vinyl monomer and 0～15 weight part of the polyolefin resin of 100 weight parts, 0～15 weight part is joined in the organic solvent, progressively heat up, and stir, form 5%～15% homogeneous solution, after drum nitrogen is got rid of oxygen, divide and progressively add 0.02～10.0 weight part initiator 3～5 times, holding temperature reaction 2～4 hours, after reaction finishes, reaction soln is lowered the temperature, solid is separated out, after filtration, obtain graft polyolefin after the drying.
Described organic solvent comprises dimethylbenzene, toluene, trichlorobenzene, chloroform.
Described fusion-grafting method comprises the steps: second olefinic monomer that contains multi-functional vinyl monomer, 0～15 weight part of the polyolefin resin of 100 weight parts, 0～15 weight part and 0.02～10.0 weight part initiator are joined after high-speed mixing in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or the mill, under 130 ℃～250 ℃, carry out melting graft reaction, reaction 1min～30min, with product cooling, pelletizing, make graft polyolefin.
The structural formula of described polyfunctional group organic coupling agent is as follows: R, represent the primary structure of polyfunctional group coupling agent
Alkyl, aryl, aralkyl, oligopolymer or contain various heteroatomic organic structures;
F represents various functional functional groups, comprises carboxyl, primary amine groups, secondary amine, hydroxyl, epoxy group(ing), isocyanate group, amide group, sulfonic group, acid chloride group;
N represents the number of functional group, n 〉=1.
Described oxidation inhibitor comprises 2,6-di-t-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2,4, one or more among 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, oxidation inhibitor B215 and the oxidation inhibitor B225.
Described solution grafting comprises the steps: the graft polyolefin and the oxidation inhibitor of preparation are joined in the polyolefine solvent, progressively heat up, and stir, form 5%～15% homogeneous solution, after drum nitrogen is got rid of oxygen, disposable adding contains multi-functional organic coupling agent, holding temperature reaction 0.1～1 hour, reaction after finishing is lowered the temperature reaction soln, solid is separated out, after filtration, obtain the coupling polyolefine after the drying.
Described polyolefine solvent comprises dimethylbenzene, toluene, trichlorobenzene, chloroform.
Described fusion-grafting method comprises the steps: graft polyolefin, oxidation inhibitor and to contain multi-functional organic coupling agent even in high-speed mixer and mixing, join then in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or the mill, under 130 ℃～250 ℃, carry out frit reaction, reaction 1min～30min, with product cooling, pelletizing, make the coupling polyolefine.
Compared with prior art, the present invention is by solution graft copolymerization reaction or melting graft reaction, under action of evocating, make to contain multi-functional vinyl monomer carry out graft reaction at a certain temperature with polyolefine under the synergy of second olefinic monomer, the preparation side chain has the graft polyolefin of functional group.By solution reaction or frit reaction, utilize multi-functional organic coupling agent to make prepared graft polyolefin coupling obtain the polyolefine of link coupled, long shootization at a certain temperature then.Can produce high-intensity long shootization polyolefine in this way, its coupling degree is controlled, with low cost, the productivity height.The polyolefine that can prepare various coupling degree according to different service requirementss, the coupling polyolefine for preparing with this method can be widely used in foam material, tubing, cable, thermoplastic elastomer, beverage bottle and sheet material etc.
Embodiment
The mensuration of polyfunctional group vinyl monomer percentage of grafting in the graft polyolefin
That adopts the resulting graft polyolefin of examination of infrared spectrum contains polyfunctional group vinyl monomer percentage of grafting, measures the relative intensity of characteristic peak before and after its extraction, according to langbobier law, can obtain reaction efficiency.Calculation formula is:
Reaction efficiency=100%*C
2/ (1-C
1)
Wherein, C
1---the concentration of polyfunctional group grafted monomer in the proportioning;
C
2---the concentration of extraction back polyfunctional group grafted monomer
1-C
1---polyolefinic concentration before the extraction is polyolefinic initial charge.
The mensuration of coupling polyolefin melt flow rate (MFR)
MFR, measures under the 2.16kg load at 230 ℃ with SRSY-1 melt flow rate (MFR) determinator.
The mensuration of coupling polyolefine storage modulus
The PP sample places the vacuum tabletting machine of 200 ℃ of temperature, and compressing tablet 30min makes the thin slice that thickness is about 1mm, and the Rheostress600 rheological analysis instrument of producing with Thermo Haake is tested its storage modulus then.
Following embodiment further specifies of the present invention, rather than limits the scope of the invention:
The long shootization polyolefine of polyolefine coupling method preparation of the present invention, it is polyolefin resin by specified quantitative, specified quantitative contain multi-functional vinyl monomer, second olefinic monomer of specified quantitative, the initiator of specified quantitative obtain containing the polyolefine of side chain functionalities by solution or melting graft reaction.And then utilize containing of specified quantitative of multi-functional organic coupling agent and the oxidation inhibitor of specified quantitative, the method by solution or molten chemical reaction obtains.
Raw material and consumption that the coupling polyolefine that uses polyolefine coupling method of the present invention to prepare is adopted are as follows:
The polyolefin resin of (1) 100 part (parts by weight) comprises the multipolymer of polypropylene, polyethylene or ethylene, propylene, and its melt flow rate (MFR) is between 0.1g/10min～50g/10min, and preferred melt flow rate (MFR) is 1g/10min～30g/10min.Melt flow rate (MFR) is too big or too little, all is unfavorable for polyolefin resin and the reaction that contains multi-functional vinyl monomer, thereby reduces reaction efficiency, influences the polyolefinic cladodification rate of final coupling.So further preferred polyolefin melt flow rate is 3g/10min～20g/10min.
(2) 0.1～25 parts (weight part) contain multi-functional vinyl monomer, comprise in vinylformic acid, maleic anhydride, methacrylic acid, fumaric acid, methylene-succinic acid, undecylenic acid, glycidyl methacrylate, acrylamide, N hydroxymethyl acrylamide, Hydroxyethyl acrylate, the Propylene glycol monoacrylate one or several.Addition is preferably 2～18 parts, more preferably 3～12 parts.If the consumption of grafted monomer, can make the more homopolymer of generation between the grafted monomer greater than 25 parts, influence the polyolefinic performance of coupling; If but the addition of polyfunctional monomer then is difficult to reach the link coupled purpose less than 0.1 part.
Second olefinic monomer of (3) 0～25 parts (weight part) comprises one or more of methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, vinylbenzene, Vinylstyrene, alpha-methyl styrene.Addition is preferably 2～18 parts, more preferably 3～12 parts.Add olefinic monomer and can improve the reaction efficiency that contains multi-functional vinyl monomer on the one hand, can suppress polyolefinic degraded on the other hand.If but the consumption of olefinic monomer can make second olefinic monomer produce more homopolymer greater than 25 parts, influences the polyolefinic performance of coupling.
The initiator of (4) 0.02～10.0 parts (weight part), comprise dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, tert butyl peroxy benzoate, 1, one or several of peroxide initiator such as two (tert-butyl hydroperoxide sec.-propyl) benzene of 4-and azobisisobutyronitrile, azo two eyeball in different heptan etc.If the consumption of initiator is lower than 0.02 part (weight part), the number of free radical of generation is too low, can reduce polyfunctional group vinyl monomer and polyolefinic reaction efficiency, influences the polyolefinic use properties of coupling.If but the consumption of initiator then can cause the crosslinked and DeR that polyolefine is serious greater than 10.0 parts (weight parts), in addition, remaining initiator also can worsen the polyolefinic performance of coupling.
(5) polyolefinic graft reaction can be undertaken by solution reaction and two kinds of methods of frit reaction:
Solution reaction is that the various materials except that initiator are joined in the organic solvents such as dimethylbenzene, toluene, trichlorobenzene, chloroform, progressively is warming up to 100～145 degree, and stirs, and forms 5%～15% homogeneous solution.After drum nitrogen is got rid of oxygen, divide progressively to add initiator 3～5 times holding temperature reaction 2～4 hours.After reaction finished, with the reaction soln cooling, solid was separated out, after filtration, obtain graft polyolefin after the drying.
In solution reaction, if temperature of reaction is lower than 100 ℃, polyolefine may dissolve not exclusively, makes graft reaction be difficult to carry out.If temperature of reaction is too high, the violent boiling of solvent can not stablize graft reaction to carry out.
Frit reaction is that various materials are joined after high-speed mixing in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers, the mill, in 130 ℃～250 ℃ scopes, carry out frit reaction, carry out frit reaction in more preferably 120 ℃～200 ℃ scopes, reaction times is 1min～30min, more preferably 3min～8min.With product cooling, pelletizing, make graft polyolefin.
In frit reaction, if temperature of reaction is lower than 100 ℃, polyolefine fusion fully, graft reaction is difficult to carry out.If temperature of reaction is higher than 250 ℃, not only can reduce polyolefinic percentage of grafting and also can make the polyolefin product degraded, worsen its physicals.If the reaction times, graft reaction can not carry out fully, influences polyolefinic percentage of grafting less than 1min, residual initiator also can worsen the performance of polyolefin product.If the reaction times, then might make the polyolefine degraded greater than 30min.
The graft polyolefin resin of (6) 100 parts (weight part), it is to prepare by above-mentioned polyolefine grafting method.
(7) 0.1～20 parts (weight part) contains multi-functional organic coupling agent, and structural formula is as follows:
R represents the primary structure of polyfunctional group coupling agent, as alkyl, aryl, aralkyl, oligopolymer or contain various heteroatomic organic structures.For solution reaction, preferably use the organism of R as alkyl; React the organism that preferred R is oligopolymer or aralkyl for melt blending, can strengthen the consistency that contains polyfunctional group organic coupling agent and graft polyolefin like this, linked reaction is carried out smoothly.
F, represent various functional functional groups, as carboxyl, primary amine groups, secondary amine, hydroxyl, epoxy group(ing), isocyanate group, amide group, sulfonic group, acid chloride group etc., the preferred functional group of F that use as primary amine groups, carboxyl, further preferably use the functional group of F, can accelerate to contain the speed of response of polyfunctional group organism and graft polyolefin like this as primary amine groups.
N represents the number of functional group, n 〉=1, and preferred n=2, can effectively control polyolefinic coupling degree this moment, if n is too little, may not produce linked reaction, if n is too big, can make linked reaction out of hand, worsens the polyolefinic performance of coupling.
The antioxidant content of (8) 0～10 parts (weight part), comprise 2,6-di-t-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2,4, one or more among 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, oxidation inhibitor B215 and the oxidation inhibitor B225.The adding of oxidation inhibitor can be regulated polyolefinic response situation of coupling and fluidity of molten, if still add-on can worsen the polyolefinic use properties of coupling greater than 10 parts.
(9) can adopt following two kinds of methods to carry out the coupling of graft polyolefin usually, thereby obtain coupling polyolefine of the present invention.
1) solution reaction method: according to the batching that above illustrates, the graft polyolefin for preparing is according to the method described above joined in the organic solvents such as dimethylbenzene, toluene, trichlorobenzene, chloroform, progressively heat up, and stir, form 5%～15% homogeneous solution.After drum nitrogen is got rid of oxygen, will contain that multi-functional organism is disposable to join in the solution, holding temperature reaction 0.5～1 hour.After reaction finished, with the reaction soln cooling, solid was separated out, after filtration, obtain the coupling polyolefine after the drying.
2) frit reaction method: according to the batching that above illustrates; with graft polyolefin, the oxidation inhibitor of preparation according to the method described above and contain multi-functional organism and after high-speed mixing, progressively join in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers, the mill; in 160 ℃～190 ℃ following frit reactions; time is 1min～30min; granulation after pelletizing or pulverizing promptly obtains the coupling polyolefine.
Embodiment and reference examples:
Embodiment and reference examples 1～2nd, in solution, carry out the polyacrylic preparation of long shootization:
Embodiment 1: get polypropylene EPS30R (Qilu Petrochemical limited-liability company) 100 grams, 1010 oxidation inhibitor, 0.1 gram joins in the flask of 2000ml, adds 1300 gram dimethylbenzene then, progressively is warming up to 140 ℃.After treating that solid all dissolves, add acrylic acid-grafted monomer 2 grams, vinylbenzene 2 grams divided 0.36 gram benzoyl peroxide to join in the flask for 5 times then in 30 minutes, keep 140 ℃ of reactions.Reaction is cooled to room temperature with flask after finishing, and adds 100 gram acetone, after stirring treats that solid is separated out fully, is placed on drying in the vacuum drying oven, obtains graft polyolefin.Vinylformic acid and polyacrylic percentage of grafting the results are shown in Table 1.
Get the graft polypropylene of 50g by method for preparing, 1010 oxidation inhibitor, 0.05 gram joins in the flask of 2000ml, adds 1000 gram dimethylbenzene then, progressively is warming up to 140 ℃.Treat solid all after the dissolving, 1.4 grams, 1,4 butanediol diglycidyl ether is divided in 30 minutes as the polyfunctional group coupling agent join in the flask for 5 times, keep 140 ℃ of reactions.Reaction is cooled to room temperature with flask after finishing, and adds 100 gram acetone, after stirring treats that solid is separated out fully, is placed on drying in the vacuum drying oven, obtains the long shootization polyolefine.The polyolefinic every performance of long shootization is listed in the table 1.
Reference examples 1: the graft polypropylene of getting 50g embodiment 1 preparation.The coupling method of graft polypropylene is identical with embodiment 1, just 1.2 gram ethylene glycol diglycidylethers is joined as coupling agent and carries out linked reaction in the graft polypropylene solution.The polyacrylic every performance of the long shootization that obtains is listed in the table 1.
Embodiment 2: its polypropylene grafted method is identical with embodiment 1, just hydroxyethyl methylacrylate is carried out graft reaction as grafted monomer and polypropylene.Its coupling method is also identical with embodiment 1, just 0.65 gram hexamethylene diisocyanate (HDI) is joined as coupling agent and carries out linked reaction in the graft polypropylene solution.Hydroxyethyl methylacrylate and polyacrylic percentage of grafting result and the polyolefinic every performance of long shootization that obtains are listed in the table 1.
Reference examples 2: the graft polypropylene of getting 50g embodiment 2 preparations.The coupling method of graft polypropylene is identical with embodiment 1, and just with 0.67 gram Toluene-2,4-diisocyanate, 4-vulcabond (TDI) joins as coupling agent and carries out linked reaction in the graft polypropylene solution.The polyacrylic every performance of the long shootization that obtains is listed in the table 1.
Embodiment and reference examples 3～4th, adopt scorification to carry out the polyacrylic preparation of long shootization:
Embodiment 3: get 10 kilograms of polypropylene EPS30R (Qilu Petrochemical limited-liability company), 0.2 kilogram of GMA grafted monomer, 0.2 kilogram of vinylbenzene, dicumyl peroxide 36 grams, dicumyl peroxide is dissolved in GMA and the cinnamic monomer, all put into high-speed mixer then and mixed discharging 2 minutes.Compound is joined in the twin screw extruder that is preheating to 170 ℃, extrude with the tachyphylaxis of 50rpm.Extrude product and after pelletizing, obtain graft polyolefin.GMA and polyolefinic percentage of grafting the results are shown in Table 1.
Get 5 kilograms of graft polypropylenes by method for preparing, oxidation inhibitor 20 grams, hexanediamine 40.8 grams are all put into high-speed mixer then and were mixed discharging 2 minutes.Compound is joined in the twin screw extruder that is preheating to 180 ℃, extrude with the tachyphylaxis of 80rpm.Extrude product and after pelletizing, obtain the coupling polyolefine.The polyolefinic every performance of long shootization is listed in the table 2.
Reference examples 3: the graft polypropylene of getting 5 kilograms of embodiment, 3 preparations.The coupling method of graft polypropylene is identical with embodiment 3, just 31.0 gram butanediamine is joined as coupling agent and carries out linked reaction in the graft polypropylene.The polyacrylic every performance of the long shootization that obtains is listed in the table 2.
Embodiment 4: its polypropylene grafted method is identical with embodiment 3, just maleic anhydride is carried out graft reaction as grafted monomer and polypropylene.Its coupling method is also identical with embodiment 3, just 74.5 gram ethohexadiols is joined as coupling agent and carries out linked reaction in the graft polypropylene.Maleic anhydride and polyacrylic percentage of grafting result and the polyolefinic every performance of long shootization that obtains are listed in the table 2.
Reference examples 4: the graft polypropylene of getting 5 kilograms of embodiment, 4 preparations.The coupling method of graft polypropylene is identical with embodiment 4, just 32.7 gram ethylene glycol is joined as coupling agent and carries out linked reaction in the graft polypropylene.The polyacrylic every performance of the long shootization that obtains is listed in the table 2.
Table 1
As can be seen from Table 1, with vinylformic acid and hydroxyethyl methylacrylate can with polypropylene generation graft reaction, and percentage of grafting is all than higher, and hydroxyethyl methylacrylate is than acrylic acid percentage of grafting height, this may be hydroxyethyl methylacrylate with polyacrylic consistency than the better cause of vinylformic acid.
Carry out the polyacrylic melt flow rate (MFR) of link coupled long shootization with 1,4 butanediol diglycidyl ether and HDI and be lower than EPS30R, storage modulus is higher than EPS30R, illustrates through the polypropylene after these two kinds of coupling agent couplings to have obtained effective cladodification.And the polyacrylic performance after spent glycol diglycidylether and the TDI coupling is worsened.This is because the molecular chain of back two kinds of coupling agents is shorter, by the polypropylene molecular chain embedding, causes linked reaction not carry out when linked reaction.And long coupling agent can carry out linked reaction between different polypropylene molecular chain, makes polypropylene produce cladodification.
Table 2
From table 2 equally as can be seen, GMA and maleic anhydride and polypropylene have good graft effect, and both grafting efficiencies have reached 80%.And hexanediamine and ethohexadiol with backbone can make graft polypropylene produce good coupling effect.
Claims (10)
1. the coupling method of a molecular polyolefin chain, it is characterized in that, this method is by solution graft copolymerization reaction or melting graft reaction, under 0.02～10.0 weight part action of evocating, make 0～15 weight part contain multi-functional vinyl monomer and carry out graft reaction at a certain temperature with 100 weight part polyolefine under 0～15 weight part, second olefinic monomer synergy, the preparation side chain has the graft polyolefin of functional group; Get the graft polyolefin of 100 weight parts,, add the polyfunctional group organic coupling agent of 0.1～20 weight part and the oxidation inhibitor of 0～10.0 weight part at a certain temperature described graft polyolefin is carried out coupling by solution reaction or melt blending reaction.
2. the coupling method of a kind of molecular polyolefin chain according to claim 1 is characterized in that, described polyolefine comprises the multipolymer of general purpose polypropylene, general polyethylene or ethylene, propylene, and its melt flow rate (MFR) is 0.1g/10min～50g/10min; Describedly contain multi-functional vinyl monomer and comprise in vinylformic acid, maleic anhydride, methacrylic acid, fumaric acid, methylene-succinic acid, undecylenic acid, glycidyl methacrylate, acrylamide, N hydroxymethyl acrylamide, Hydroxyethyl acrylate, the Propylene glycol monoacrylate one or several; Described second olefinic monomer comprises one or more in vinylbenzene, Vinylstyrene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, butyl acrylate, the butyl methacrylate; Described initiator comprises dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, tert butyl peroxy benzoate, 1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 4-, perhaps one or several in azobisisobutyronitrile, azo two eyeball in different heptan.
3. the coupling method of a kind of molecular polyolefin chain according to claim 1, it is characterized in that, described solution grafting comprises the steps: the polyolefin resin with 100 weight parts, second olefinic monomer that contains multi-functional vinyl monomer and 0～15 weight part of 0～15 weight part joins in the organic solvent, progressively heat up, and stir, form 5%～15% homogeneous solution, after drum nitrogen is got rid of oxygen, divide and progressively add 0.02～10.0 weight part initiator 3～5 times, holding temperature reaction 2～4 hours, reaction after finishing is lowered the temperature reaction soln, solid is separated out, after filtration, obtain graft polyolefin after the drying.
4. the coupling method of a kind of molecular polyolefin chain according to claim 3 is characterized in that, described organic solvent comprises dimethylbenzene, toluene, trichlorobenzene, chloroform.
5. the coupling method of a kind of molecular polyolefin chain according to claim 1, it is characterized in that, described fusion-grafting method comprises the steps: the polyolefin resin with 100 weight parts, 0～15 weight part contain multi-functional vinyl monomer, second olefinic monomer of 0～15 weight part and 0.02～10.0 weight part initiator join Haake after high-speed mixing, single screw extrusion machine, twin screw extruder, Banbury mixer, in banbury mixers or the mill, under 130 ℃～250 ℃, carry out melting graft reaction, reaction 1min～30min, product is cooled off, pelletizing makes graft polyolefin.
6. the coupling method of a kind of molecular polyolefin chain according to claim 1 is characterized in that, the structural formula of described polyfunctional group organic coupling agent is as follows:
R represents the primary structure of polyfunctional group coupling agent, comprises alkyl, aryl, aralkyl, oligopolymer or contains various heteroatomic organic structures;
F represents various functional functional groups, comprises carboxyl, primary amine groups, secondary amine, hydroxyl, epoxy group(ing), isocyanate group, amide group, sulfonic group, acid chloride group;
N represents the number of functional group, n 〉=1.
7. the coupling method of a kind of molecular polyolefin chain according to claim 1, it is characterized in that, described oxidation inhibitor comprises 2,6-di-t-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2,4, one or more among 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, oxidation inhibitor B215 and the oxidation inhibitor B225.
8. the coupling method of a kind of molecular polyolefin chain according to claim 1, it is characterized in that, described solution grafting comprises the steps: the graft polyolefin and the oxidation inhibitor of preparation are joined in the polyolefine solvent, progressively heat up, and stir, form 5%～15% homogeneous solution, after drum nitrogen is got rid of oxygen, disposable adding contains multi-functional organic coupling agent, holding temperature reaction 0.1～1 hour, reaction after finishing is lowered the temperature reaction soln, solid is separated out, after filtration, obtain the coupling polyolefine after the drying.
9. the coupling method of a kind of molecular polyolefin chain according to claim 8 is characterized in that, described polyolefine solvent comprises dimethylbenzene, toluene, trichlorobenzene, chloroform.
10. the coupling method of a kind of molecular polyolefin chain according to claim 1, it is characterized in that, described fusion-grafting method comprises the steps: graft polyolefin, oxidation inhibitor and to contain multi-functional organic coupling agent even in high-speed mixer and mixing, join then in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or the mill, under 130 ℃～250 ℃, carry out frit reaction, reaction 1min～30min, with product cooling, pelletizing, make the coupling polyolefine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101713114A CN101450982B (en) | 2007-11-29 | 2007-11-29 | Couple method of polyolefin molecular chain |
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| WO2010099645A1 (en) * | 2009-03-02 | 2010-09-10 | 上海富元塑胶科技有限公司 | Method for coupling polyolefin chains |
| CN101985490A (en) * | 2010-05-17 | 2011-03-16 | 北京中技惠民科技发展有限公司 | Method for preparing cauliflower-shaped macromolecule function materials |
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| CN102617801A (en) * | 2012-03-23 | 2012-08-01 | 哈尔滨隆华艺达包装制品有限公司 | Dimonosomic grafting master batch compatibilizer and preparation method thereof |
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| CN107282124A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of catalyst for ethylene tetramerization composition and four poly- methods |
| CN107282130A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization composition and its application |
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| CN101985490B (en) * | 2010-05-17 | 2012-07-04 | 北京中技惠民科技发展有限公司 | Method for preparing cauliflower-shaped macromolecule function materials |
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| CN107282130A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization composition and its application |
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| CN107282122B (en) * | 2016-03-31 | 2019-12-24 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and application thereof |
| CN107282124B (en) * | 2016-03-31 | 2019-12-24 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and tetramerization method |
| CN107282121B (en) * | 2016-03-31 | 2019-12-24 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization and oligomerization method |
| CN107417860A (en) * | 2017-08-29 | 2017-12-01 | 太原科技大学 | A kind of preparation method of the graft polymers of polybutene 1 |
| CN109808266A (en) * | 2019-01-08 | 2019-05-28 | 东莞辰越新材料科技有限公司 | A kind of amorphous alloy bulletproof composite material and preparation method thereof |
| CN113429521A (en) * | 2021-07-20 | 2021-09-24 | 汕头市三马塑胶制品有限公司 | High-melt-strength polypropylene and preparation method thereof |
| CN115181359A (en) * | 2022-07-28 | 2022-10-14 | 江苏金发科技新材料有限公司 | Low-warpage glass fiber reinforced polypropylene material and preparation method thereof |
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