CN103897106B - The method improving polyolefin graft unsaturated carboxylic acid monomer percent grafting - Google Patents
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Abstract
The present invention is to provide a kind of method improving polyolefin graft unsaturated carboxylic acid monomer percent grafting.Unsaturated carboxylic acid monomer is prepared by acryloyl chloride or methacrylic chloride and the reaction in the basic conditions of corresponding aminoacid；By unsaturated carboxylic acid monomer and cerous chloride or its hydrate be dissolved in N simultaneously, N-dimethylformamide or obtain solution A in water；Dibenzoyl peroxide is dissolved in dimethylbenzene and obtains solution B；Polyolefin particles and styrene are placed in the reaction vessel of water；Joining in reaction vessel by solution A and solution B, stirring 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filtration, dry.The present invention adds cerous chloride and hydrate thereof in reaction system, due to the valence shell structure that rare-earth element cerium is unique, monomer can be made to activate by the coordination between the carbonyl in unsaturated carboxylic acid monomer structure, therefore improve its graft reaction activity, and then improve the percent grafting of graft product.
Description
Technical field
The present invention relates to a kind of Graft Modification of Polyolefine method, particularly to improving the method that aqueous-phase suspending solid phase grafting method prepares unsaturated carboxylic acid functionalised polyolefin percent grafting.
Background technology
It is broad-spectrum general-purpose plastics with the polyolefin that polypropylene (PP) and polyethylene (PE) are representative, have that yield is big, price is low, water-fast, chemical-resistant resistance, and the advantage such as moulding process is good, have become as the commercial materials that a kind of power of influence is big and versatility is strong.Continuous progressive along with catalysis technique, has synthesized controlled molecular structure and the high polyolefine material of serviceability, has been widely used in the industries such as article of everyday use, packaging, automobile, building and household electrical appliance.
But due to the nonpolar and crystallinity that polyolefine material is intrinsic, when making they and other material such as polar polymer, inorganic filler and metal are blended, interface interaction power is poor, need to add compatilizer to reduce interfacial tension during compound use, increases interfacial adhesion.Their dyeability, cementability, antistatic behaviour, hydrophilic are also very poor simultaneously, which has limited the application of polyolefine material, constrain the further development of polyolefine material.Polyolefin being carried out functional modification by structural design, it is possible to improve the compatibility between this type of material and other materials and cohesive force, thus having widened the range of application of polyolefine material, and designing the material of applicable industry requirement according to special requirement.The technology of the functional polyolefin based on graft modification is achieved with satisfied result at present, and polyolefinic grafting modification has become as the technological approaches producing high value added product.
Graft Modification of Polyolefine method mainly has: solution graft copolymerization, fusion-grafting, radiation grafting, solid phase grafting, Suspension Graft.Wherein first three methods needs to carry out under high-energy radiation or hot conditions, and molecular polyolefin chain is easy to occur chain rupture to degrade, and after this makes graft modification, the performance of material significantly decreases.Solid phase grafting method and Suspension Graft Method carry out graft reaction at a lower temperature, polyolefin palliating degradation degree is made substantially to reduce, wherein aqueous-phase suspending solid phase grafting method polyolefin is suspended in containing initiator, interfacial agents, grafted monomers aqueous solution in carry out grafting, there is the advantages such as reaction temperature is low, the response time is short, production cost is low, reaction process is simple, post processing is easy, also can cohere, stir and conduct heat the deficiency such as uneven efficiently against the material that conventional solid Graft Method easily occurs.
Graft Modification of Polyolefine monomer conventional at present mainly has maleic anhydride (MAH), glycidyl methacrylate (GMA), acrylic acid (AA), methyl methacrylate (MMA), N-N-cyclohexylmaleimide etc., these monomers often toxicity is big, boiling point is low, volatile or distillation, eyes and skin to site operation personnel bring damage, there is very big difficulty in actual production process.
The applicant of the present invention have developed a class unsaturated carboxylic acid monomer, and it is applied to the graft modification of polypropylene and linear low density polyethylene, it is prepared for Novel polypropylene and the linear low density polyethylene graft copolymer of high percent grafting, associated open file is shown in the Chinese patent application file CN201210066164.5 (application on March 14th, 2012) of applicant, CN201210417754.8 (application on October 29th, 2012), CN201310125153.4 (application on April 11st, 2013) and CN201310131982.3 (application on April 16th, 2013).Compared with traditional polyolefin graft monomer (such as maleic anhydride, glycidyl methacrylate, acrylic acid, methacrylic acid, methyl methacrylate etc.), such unsaturated carboxylic acid monomer have nonhazardous, non-volatile or distillation and because having good biocompatibility containing amino acid residue, these advantages are expected to make polyolefin manifest on biological field and are more widely applied prospect.
In above-mentioned Chinese invention patent application file, CN201210066164.5 (application on March 14th, 2012) and CN201310125153.4 (application on April 11st, 2013) adopts solid phase grafting method to be prepared for polypropylene and the linear low density polyethylene graft copolymer of high percent grafting, but when adopting the method to prepare high-density polycthylene grafted copolymer, then cannot obtain graft copolymer, this is likely due to the compound with regular structure of high density polyethylene (HDPE), degree of crystallinity is high, amorphous area proportion is significantly lower than polypropylene and Low Density Polyethylene, and graft reaction typically occurs in the amorphous area of matrix resin.
Summary of the invention
It is an object of the invention to provide one and can improve graft reaction activity, and then improve the method improving polyolefin graft unsaturated carboxylic acid monomer percent grafting of the percent grafting of graft product.
The object of the present invention is achieved like this:
(1) unsaturated carboxylic acid monomer is prepared by acryloyl chloride or methacrylic chloride and the reaction in the basic conditions of corresponding aminoacid；
(2) cerous chloride or its hydrate of unsaturated carboxylic acid monomer that weight is 5-25 part and 5-25 part are dissolved in 60 parts of DMFs (DMF) or water simultaneously, stir and obtain solution A in 30 minutes；2 parts of dibenzoyl peroxides (BPO) are dissolved in 10-20 part interfacial agents dimethylbenzene and obtain solution B；Being placed in the reaction vessel containing 300 parts of water by 100 parts of polyolefin particles and 5-25 part the second grafted monomers styrene (St), stirring makes polyolefin particles suspend in water equably；Joining in reaction vessel by solution A and solution B, stirring 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filtration, dry, namely obtain final graft product.
The present invention can also include:
1, described aminoacid includes proline, glycine, phenylglycine, phenylalanine or valine, the unsaturated carboxylic acid monomer respectively 1-acryloyl pyrrolidine-2-carboxylic acid of correspondence, 1-methacryl pyrrolidine-2-carboxylic acid, 2-acrylamide guanidine-acetic acid, 2-methacryl glycine, 2-acrylamido-2-phenylacetic acid, 2-methacryl amido-2-phenylacetic acid, 2-acrylamido-3-phenylpropionic acid, 2-methacryl amido-3-phenylpropionic acid, 2-acrylamido-3 Methylbutanoic acid or 2-methacryl amido-3 Methylbutanoic acid.
2, the mol ratio of unsaturated carboxylic acid monomer and cerous chloride or its hydrate is 1:3 to 3:1, it is preferable that 1:1.
3, unsaturated carboxylic acid graft monomer and the auxiliary cinnamic weight ratio of grafted monomers are 3:7 to 7:3, it is preferable that 1:1.
Multiple (methyl) acrylamide derivative class unsaturated carboxylic acid monomer is applied to the graft modification of polyolefin (including polypropylene, linear low density polyethylene, high density polyethylene (HDPE)) by the present invention, adopt aqueous-phase suspending solid phase grafting method, adding cerous chloride or its hydrate in reaction system, preparation has the polyolefin graft copolymer of high percent grafting and good biocompatibility.
The present invention is when preparing unsaturated carboxylic acid functionalised polyolefin, reaction system is added cerous chloride and hydrate thereof, due to the valence shell structure that rare-earth element cerium is unique, monomer can be made to activate by the coordination between the carbonyl in unsaturated carboxylic acid monomer structure, therefore improve its graft reaction activity, and then improve the percent grafting of graft product.
In order to obtain pure graft product, graft product is stripped by the present invention respectively with methanol and acetone, purpose is to remove grafted monomers and cinnamic homopolymer, copolymer and unreacted monomer and other auxiliary agents, then through vacuum drying, can obtain final graft product.
Compared with prior art, the present invention has the feature that
1) present invention adds cerous chloride or its hydrate in polyolefin graft unsaturated carboxylic acid system, utilize the coordination of rare-earth element cerium and unsaturated carboxylic acid monomer, improve the reactivity of monomer, greatly improve the percent grafting of polyolefin (especially high density polyethylene (HDPE)) graft copolymer；
2) methacrylamide derivatives class unsaturated carboxylic acid monomer is applied to polyolefinic functionalization and modification by the present invention first, obtain the functionalised polyolefin copolymer of high percent grafting, such unsaturated carboxylic acid monomer to the present inventor it have been reported that acrylamide derivative class unsaturated carboxylic acid (related application see the present inventor) similar, the advantage with nonhazardous, good biocompatibility, by above-mentioned two class monomer applications and polyolefinic functionalization and modification, greatly improve the polyolefin application prospect at biological field.
Accompanying drawing explanation
Fig. 1 is HDPE and the infrared spectrogram of unsaturated carboxylic acid monomer grafting HDPE.In figure, a is the infrared spectrogram of HDPE, and b is the infrared spectrogram of unsaturated carboxylic acid monomer grafting HDPE, and c is the infrared spectrogram of the unsaturated carboxylic acid monomer grafting HDPE attaching cerous chloride hydrate.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.The scope of the present invention is not restricted by the embodiments.
Comparative example 1:
Respectively the unsaturated carboxylic acid monomer 1-methacryl amido-2-phenylacetic acid that weight is 10 parts is dissolved in 60 parts of N,N-dimethylformamides (DMF), 2 parts of dibenzoyl peroxides (BPO) are dissolved in 20 parts of interfacial agents dimethylbenzene；Being placed in the reaction vessel containing 300 parts of water by 100 parts of high density polyethylene (HDPE) (HDPE) granules and 10 part of second grafted monomers styrene (St), stirring makes HDPE granule suspend in water equably；Unsaturated carboxylic acid monomer solution and BPO solution are joined in reaction vessel by syringe, 1.5h is stirred under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtain final graft product, and its percent grafting is 2.9%.
The present invention adopts the percent grafting of chemical titration unsaturated carboxylic acid monomer grafting HDPE.Concrete grammar is as follows: first by graft product respectively with acetone and methanol extracting 12h, to remove the styrene and unsaturated carboxylic acid homopolymer being likely to residual.Accurately weighing the graft product of a certain amount of (m), be dissolved in appropriate dimethylbenzene, adding excessive concentration is C1KOH-ethanol standard solution V1ML, reflux 1h at 120 DEG C.After question response is abundant, with concentration for C2The anti-excess base that drips of acetic acid-dimethylbenzene standard solution, consumption volume is V2ML, is calculated as follows out percent grafting (every time measuring parallel three samples):
In formula, M is the molal weight of unsaturated carboxylic acid monomer.
By calculating it can be seen that the percent grafting of the present embodiment unsaturated carboxylic acid monomer grafting HDPE is 2.9%.
Embodiment 1:
By unsaturated carboxylic acid monomer 1-methacryl amido-2-phenylacetic acid that weight is 10 parts and 10 parts of cerous chloride heptahydrate (CeCl3·7H2O) it is dissolved in 60 parts of DMFs (DMF) simultaneously, stirs 30 minutes (solution 1)；2 parts of dibenzoyl peroxides (BPO) are dissolved in 20 parts of interfacial agents dimethylbenzene (solution 2)；Being placed in the reaction vessel containing 300 parts of water by 100 parts of high density polyethylene (HDPE) (HDPE) granules and 10 part of second grafted monomers styrene (St), stirring makes HDPE granule suspend in water equably；Joining in reaction vessel by solution 1 and solution 2 by syringe, stir 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtaining final graft product, its percent grafting is 8.1%.
Comparative example 2:
Respectively the unsaturated carboxylic acid monomer 2-acrylamide guanidine-acetic acid that weight is 6 parts is dissolved in 60 parts of water, 2 parts of dibenzoyl peroxides (BPO) are dissolved in 10 parts of interfacial agents dimethylbenzene；Being placed in the reaction vessel containing 300 parts of water by 100 parts of polypropylene (PP) granules and 14 part of second grafted monomers styrene (St), stirring makes PP granule suspend in water equably；Unsaturated carboxylic acid monomer solution and BPO solution are joined in reaction vessel by syringe, 1.5h is stirred under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtain final graft product, and its percent grafting is 2.4%.
Embodiment 2:
By unsaturated carboxylic acid monomer 2-acrylamide guanidine-acetic acid that weight is 6 parts and 6 parts of CeCl3·7H2O is dissolved in 60 parts of water simultaneously, stirs 30 minutes (solution 1)；2 parts of dibenzoyl peroxides (BPO) are dissolved in 10 parts of interfacial agents dimethylbenzene (solution 2)；Being placed in the reaction vessel containing 300 parts of water by 100 parts of PP granules and 14 part of second grafted monomers styrene (St), stirring makes PP granule suspend in water equably；Joining in reaction vessel by solution 1 and solution 2 by syringe, stir 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtaining final graft product, its percent grafting is 3.1%.
Comparative example 3:
Respectively the unsaturated carboxylic acid monomer 2-acrylamido-3-phenylpropionic acid that weight is 14 parts is dissolved in 60 parts of DMFs (DMF), 2 parts of dibenzoyl peroxides (BPO) are dissolved in 20 parts of interfacial agents dimethylbenzene；Being placed in the reaction vessel containing 300 parts of water by 6 part of second grafted monomers styrene (St) of 100 parts of linear low density polyethylene (LLDPE) granules, stirring makes LLDPE granule suspend in water equably；Unsaturated carboxylic acid monomer solution and BPO solution are joined in reaction vessel by syringe, 1.5h is stirred under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtain final graft product, and its percent grafting is 5.0%.
Embodiment 3:
By unsaturated carboxylic acid monomer 2-acrylamido-3-phenylpropionic acid that weight is 14 parts and 14 parts of CeCl3·7H2O is dissolved in 60 parts of DMFs (DMF) simultaneously, stirs 30 minutes (solution 1)；2 parts of dibenzoyl peroxides (BPO) are dissolved in 20 parts of interfacial agents dimethylbenzene (solution 2)；Being placed in the reaction vessel containing 300 parts of water by 6 part of second grafted monomers styrene (St) of 100 parts of LLDPE granules, stirring makes LLDPE granule suspend in water equably；Joining in reaction vessel by solution 1 and solution 2 by syringe, stir 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtaining final graft product, its percent grafting is 8.1%.
Comparative example 4:
Respectively the unsaturated carboxylic acid monomer L-1-acryloyl pyrrolidine-2-carboxylic acid that weight is 6 parts is dissolved in 60 parts of DMFs (DMF), 2 parts of dibenzoyl peroxides (BPO) are dissolved in 10 parts of interfacial agents dimethylbenzene；Being placed in the reaction vessel containing 300 parts of water by 100 parts of PP granules and 14 part of second grafted monomers styrene (St), stirring makes PP granule suspend in water equably；Unsaturated carboxylic acid monomer solution and BPO solution are joined in reaction vessel by syringe, 1.5h is stirred under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtain final graft product, and its percent grafting is 4.0%.
Embodiment 4:
By unsaturated carboxylic acid monomer L-1-acryloyl pyrrolidine-2-carboxylic acid that weight is 6 parts and 6 parts of CeCl3·7H2O is dissolved in 60 parts of DMFs (DMF) simultaneously, stirs 30 minutes (solution 1)；2 parts of dibenzoyl peroxides (BPO) are dissolved in 10 parts of interfacial agents dimethylbenzene (solution 2)；Being placed in the reaction vessel containing 300 parts of water by 100 parts of PP granules and 14 part of second grafted monomers styrene (St), stirring makes PP granule suspend in water equably；Joining in reaction vessel by solution 1 and solution 2 by syringe, stir 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtaining final graft product, its percent grafting is 5.2%.
Comparative example 5:
Respectively the unsaturated carboxylic acid monomer 2-acrylamido-3-phenylpropionic acid that weight is 6 parts is dissolved in 60 parts of DMFs (DMF), 2 parts of dibenzoyl peroxides (BPO) are dissolved in 20 parts of interfacial agents dimethylbenzene；Being placed in the reaction vessel containing 300 parts of water by 100 parts of HDPE granules and 14 part of second grafted monomers styrene (St), stirring makes HDPE granule suspend in water equably；Unsaturated carboxylic acid monomer solution and BPO solution are joined in reaction vessel by syringe, 1.5h is stirred under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtain final graft product, and its percent grafting is 2.3%.
Embodiment 5:
By unsaturated carboxylic acid monomer 2-acrylamido-3-phenylpropionic acid that weight is 6 parts and 6 parts of CeCl3·7H2O is dissolved in 60 parts of DMFs (DMF) simultaneously, stirs 30 minutes (solution 1)；2 parts of dibenzoyl peroxides (BPO) are dissolved in 20 parts of interfacial agents dimethylbenzene (solution 2)；Being placed in the reaction vessel containing 300 parts of water by 100 parts of HDPE granules and 14 part of second grafted monomers styrene (St), stirring makes HDPE granule suspend in water equably；Joining in reaction vessel by solution 1 and solution 2 by syringe, stir 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filter, respectively with methanol and acetone extraction, vacuum drying, can obtaining final graft product, its percent grafting is 4.1%.
Claims (8)
1. the method improving polyolefin graft unsaturated carboxylic acid monomer percent grafting, is characterized in that:
(1) unsaturated carboxylic acid monomer is prepared by acryloyl chloride or methacrylic chloride and the reaction in the basic conditions of corresponding aminoacid；
(2) cerous chloride or its hydrate of unsaturated carboxylic acid monomer that weight is 5-25 part and 5-25 part are dissolved in 60 parts of DMFs or water simultaneously, stir and obtain solution A in 30 minutes；2 parts of dibenzoyl peroxides are dissolved in 10-20 part interfacial agents dimethylbenzene and obtain solution B；Being placed in the reaction vessel containing 300 parts of water by 100 parts of polyolefin particles and 5-25 part the second grafted monomers styrene, stirring makes polyolefin particles suspend in water equably；Joining in reaction vessel by solution A and solution B, stirring 1.5h under 60 DEG C of nitrogen atmospheres, 95 DEG C are reacted 2 hours, then through cooling, washing, filtration, dry, namely obtain final graft product.
2. the method for raising polyolefin graft unsaturated carboxylic acid monomer percent grafting according to claim 1, is characterized in that: the mol ratio of unsaturated carboxylic acid monomer and cerous chloride or its hydrate is 1:3 to 3:1.
3. the method for raising polyolefin graft unsaturated carboxylic acid monomer percent grafting according to claim 2, is characterized in that: the mol ratio of unsaturated carboxylic acid monomer and cerous chloride or its hydrate is 1:1.
4. the method improving polyolefin graft unsaturated carboxylic acid monomer percent grafting according to claim 1,2 or 3, is characterized in that: unsaturated carboxylic acid graft monomer and the auxiliary cinnamic weight ratio of grafted monomers are 3:7 to 7:3.
5. the method for raising polyolefin graft unsaturated carboxylic acid monomer percent grafting according to claim 4, is characterized in that: unsaturated carboxylic acid graft monomer and the auxiliary cinnamic weight ratio of grafted monomers are 1:1.
6. according to claim 1, the method improving polyolefin graft unsaturated carboxylic acid monomer percent grafting described in 2 or 3, it is characterized in that: described aminoacid includes proline, glycine, phenylglycine, phenylalanine or valine, corresponding unsaturated carboxylic acid monomer respectively 1-acryloyl pyrrolidine-2-carboxylic acid, 1-methacryl pyrrolidine-2-carboxylic acid, 2-acrylamide guanidine-acetic acid, 2-methacryl glycine, 2-acrylamido-2-phenylacetic acid, 2-methacryl amido-2-phenylacetic acid, 2-acrylamido-3-phenylpropionic acid, 2-methacryl amido-3-phenylpropionic acid, 2-acrylamido-3 Methylbutanoic acid or 2-methacryl amido-3 Methylbutanoic acid.
7. the method for raising polyolefin graft unsaturated carboxylic acid monomer percent grafting according to claim 4, it is characterized in that: described aminoacid includes proline, glycine, phenylglycine, phenylalanine or valine, corresponding unsaturated carboxylic acid monomer respectively 1-acryloyl pyrrolidine-2-carboxylic acid, 1-methacryl pyrrolidine-2-carboxylic acid, 2-acrylamide guanidine-acetic acid, 2-methacryl glycine, 2-acrylamido-2-phenylacetic acid, 2-methacryl amido-2-phenylacetic acid, 2-acrylamido-3-phenylpropionic acid, 2-methacryl amido-3-phenylpropionic acid, 2-acrylamido-3 Methylbutanoic acid or 2-methacryl amido-3 Methylbutanoic acid.
8. the method for raising polyolefin graft unsaturated carboxylic acid monomer percent grafting according to claim 5, it is characterized in that: described aminoacid includes proline, glycine, phenylglycine, phenylalanine or valine, corresponding unsaturated carboxylic acid monomer respectively 1-acryloyl pyrrolidine-2-carboxylic acid, 1-methacryl pyrrolidine-2-carboxylic acid, 2-acrylamide guanidine-acetic acid, 2-methacryl glycine, 2-acrylamido-2-phenylacetic acid, 2-methacryl amido-2-phenylacetic acid, 2-acrylamido-3-phenylpropionic acid, 2-methacryl amido-3-phenylpropionic acid, 2-acrylamido-3 Methylbutanoic acid or 2-methacryl amido-3 Methylbutanoic acid.
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| CN102603982A (en) * | 2012-03-14 | 2012-07-25 | 哈尔滨工程大学 | Method for preparing unsaturated carboxylic acid grafted polypropylene copolymer |
| CN103224593A (en) * | 2013-04-16 | 2013-07-31 | 哈尔滨工程大学 | Method for grafting linear low density polyethylene to polar monomer |
| CN103483470A (en) * | 2013-09-06 | 2014-01-01 | 中国科学院化学研究所 | Terminal group-functionalized polyethylene and preparation method thereof |
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| CN102603982A (en) * | 2012-03-14 | 2012-07-25 | 哈尔滨工程大学 | Method for preparing unsaturated carboxylic acid grafted polypropylene copolymer |
| CN103224593A (en) * | 2013-04-16 | 2013-07-31 | 哈尔滨工程大学 | Method for grafting linear low density polyethylene to polar monomer |
| CN103483470A (en) * | 2013-09-06 | 2014-01-01 | 中国科学院化学研究所 | Terminal group-functionalized polyethylene and preparation method thereof |
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