CN103351453B - A kind of long-acting antistatic polypropylene segmented copolymer and synthetic method thereof and method of modifying - Google Patents
A kind of long-acting antistatic polypropylene segmented copolymer and synthetic method thereof and method of modifying Download PDFInfo
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Abstract
The present invention relates to a kind of long-acting antistatic polypropylene segmented copolymer and synthetic method thereof and method of modifying. Segmented copolymer general formula is A-B-A, A is anti-static function segment, and B is parent's matrix polypropylene segment; Anti-static function segment is: polyacrylate, poly-p styrene sulfonic acid salt, polymaleic acid salt, polystyrene-maleic salt, Polyvinylpyrolidone (PVP) or polyvinyl pyridine quaternary ammonium salt; The molecular weight of parent's matrix polypropylene segment and anti-static function segment is respectively 1000��20000g/mol. The segmented copolymer sticking power that the present invention obtains improves greatly, it is not easy to come off, and persistence is good so that antistatic property has long-acting property, and don't affects the mechanical property of body material; Gained is material modified has good antistatic property, it is possible to avoid the accumulation of static electricity on polypropylene articles surface, thus prevents the problem that produces because of product surface buildup of static electricity or accident, has huge application prospect and marketable value.
Description
Technical field
The present invention relates to copolymer field, specifically, it relates to a kind of long-acting antistatic polypropylene segmented copolymer and synthetic method thereof, and utilize the method for modifying of this long-acting antistatic polypropylene segmented copolymer.
Background technology
Since the middle and later periods fifties 20th century suitability for industrialized production, acrylic plastering (PP) has become current domestic and international application a kind of general plastics of thermoplasticity comparatively widely. The features such as polypropylene has that density is little, machine-shaping property is excellent, electrical insulation capability is good, mechanical property and good heat resistance, have a wide range of applications in fields such as automobile, building, packagings. But due to polyacrylic nonpolar structure and high electric insulation performance, its volume specific resistance is generally 1016��1018�� m, surface resistivity is 1016��1017��, in friction, stripping or induction process, material surface can produce static charge. Owing to the surface resistivity of PP own and volume specific resistance are higher, so the static charge produced cannot be shifted. So, in industrial production and practical application, polyacrylic surface very easily produces accumulation of static electricity and causes dust suction, electric shock, burning even to be exploded, and brings harm to industrial and agricultural production and daily life. Therefore, how to reduce and eliminate the static hazard of acrylic plastering and goods thereof, become the current technical task being badly in need of solving.
At present, the method for static charge eliminating the accumulation of PP surface adds static inhibitor, and static inhibitor can comprise the inorganic antistatic agent such as silver system, titanium system, graphitized carbon black, and the organic surface active agent two kinds such as quaternary ammonium salt, alcohol, alcohol ether. Although wherein inorganic antistatic agent has good antistatic effect, but exist on the high side, addition big, on defects such as the mechanical property impact of PP matrix resin are bigger, cannot use for transparent article; Small molecules organic surface active agent easily volatilizees, runs off, and long-acting property is poor, even affects the surface effect of goods.
Polymer-metallic Catalyst is a class new anti-static agent of Recent study exploitation, by itself and the polypropene blended antistatic property that can improve material.This kind of technology it is crucial that: improve the migration enrichment of static inhibitor to polypropylene articles surface and in the degree of scatter of resin surface, improve attachment state. According to state of charge, Polymer-metallic Catalyst can be divided into cationic, anionic and non-ionic type, comprises polyethylene oxide (PEO), polyquaternium, polyether ester amine and polyether ester imide (PEEA) etc. Compared with small molecules organic surface active agent, Polymer-metallic Catalyst has the advantages such as antistatic property is good, not volatilization, and its antistatic persistence also increases. But, industrial used Polymer-metallic Catalyst major part is homopolymer at present, due to bigger with the polyacrylic textural difference of matrix resin, static inhibitor very easily comes off because of the corrosion of friction or water and organic solvent after moving to product surface, material modified antistatic permanent it is greatly affected, when addition is bigger, easily affects the mechanical property of body material.
Based on industry and the demand of practical application, it is necessary to find a kind of synthesis technique simplicity, antistatic property height, persistence good, and don't affect the polypropylene surface antistatic method of the mechanical property of body material, its corresponding segmented copolymer and material modified.
Summary of the invention
In order to solve problems of the prior art, an object of the present invention is, it is provided that a kind of long-acting antistatic polypropylene segmented copolymer.
Another object of the present invention is to, it is provided that the synthetic method of a kind of described long-acting antistatic polypropylene segmented copolymer.
A further object of the present invention is, it is provided that a kind of method of modifying utilizing described long-acting antistatic polypropylene segmented copolymer.
Long-acting antistatic polypropylene segmented copolymer provided by the invention, its general formula is A-B-A, A is anti-static function segment, and B is parent's matrix polypropylene segment; Described anti-static function segment is: polyacrylate, poly-p styrene sulfonic acid salt, polymaleic acid salt, polystyrene-maleic salt, Polyvinylpyrolidone (PVP) or polyvinyl pyridine quaternary ammonium salt.
Further, described polyacrylate is sodium polyacrylate or polyacrylic acid quaternary ammonium salt, poly-p styrene sulfonic acid salt is poly (sodium 4-styrenesulfonate) salt, polymaleic acid salt is polymaleic acid sodium salt or polymaleic acid sylvite, and polystyrene-maleic salt is polystyrene-maleic sodium salt or polystyrene-maleic sylvite.
Wherein, the molecular weight of described parent's matrix polypropylene segment and anti-static function segment is respectively 1000��20000g/mol, all preferably 1000��8000g/mol.
Further, the number of repeat unit of described parent's matrix polypropylene segment is 15��400, and the number of repeat unit of anti-static function segment is 30��750.
That is, long-acting antistatic polypropylene segmented copolymer provided by the invention, has the structure shown in following formula (when described anti-static function segment is: when polyacrylate, poly-p styrene sulfonic acid salt, polymaleic acid salt, Polyvinylpyrolidone (PVP) or polyvinyl pyridine quaternary ammonium salt):
Wherein, m is the number of repeat unit of parent's matrix polypropylene segment, m=15��400; N is the number of repeat unit of anti-static function segment, n=30��750.
Wherein, R1For H or methyl; R2For H or-COONa;
R3For: COONa ,-PhSO3Na,COO-N+(CH2CH3)4,
Or, long-acting antistatic polypropylene segmented copolymer provided by the invention, has the structure shown in following formula (when described anti-static function segment is polystyrene-maleic salt):
The definition of m and n is described above.
Wherein, the molecular weight of described long-acting antistatic polypropylene segmented copolymer is 2000��40000g/mol, it is preferable that 2000��16000g/mol.
The synthetic method of described long-acting antistatic polypropylene segmented copolymer provided by the invention, comprise: cause function monomer polyreaction by parent's matrix polypropylene segment, adopt Transfer Radical Polymerization, using cuprous chloride as catalyzer, take bipyridine as part, temperature of reaction is 50��150 DEG C, and the reaction times is 4��24 hours, prepares antistatic polypropylene segmented copolymer (containing anti-static function segment); Through further quaternary ammonium reaction or with the neutralization reaction of alkali, prepare antistatic polypropylene segmented copolymer (containing anti-static function segment).
Wherein, described function monomer is: vinylformic acid, sodium p styrene sulfonate, maleic anhydride, vinylbenzene and maleic anhydride, NVP or vinyl pyridine etc.
Wherein, described alkali is sodium hydroxide or potassium hydroxide.
Wherein, temperature of reaction preferably 100 DEG C. Preferably 12 hours reaction times.
Wherein, the synthetic method of described parent's matrix polypropylene segment comprises: by polypropylene by cracking under Pintsch process or concentrated nitric acid effect, and through end group chemical modification, prepares the polypropylene (i.e. parent's matrix polypropylene segment) of double-ended halogen.
Further; the synthetic method of described parent's matrix polypropylene segment comprises: by polypropylene cracking in 350 DEG C of nitrogen protections when; preparation is containing the polypropylene of end double bond, then polypropylene and hydrogenchloride or the hydrogen bromide of end double bond are carried out addition reaction, obtains the polypropylene of double-ended halogen (chlorine or bromine).
Or, the synthetic method of described parent's matrix polypropylene segment comprises: polypropylene and concentrated nitric acid are heated to 110 DEG C of backflows, stir, cooling after reaction 16h, filtration, and the remaining nitric acid of Ex-all, obtains end carboxyl polypropylene; Being dissolved in pimelinketone by the heating of end carboxyl polypropylene again, add epoxy chloropropane and Tetrabutyl amonium bromide, backflow, stir 6h, cooling, filtration, with ethanolic extraction, obtain the polypropylene (low-molecular-weight polypropylene of band end chlorine) of double-ended halogen.
The present invention is described in further detail below: the polypropylene segment of the present invention's parent's matrix can be obtained by cracking under Pintsch process or concentrated nitric acid effect by polypropylene, the polypropylene segment of the close matrix prepared by aforesaid method can control its molecular weight and molecular weight distribution thereof, and the end of molecular chain contains the double bond or carboxyl functional group that can react further, react through further end group, chlorine is introduced in polyacrylic molecular end, the halogens such as bromine, cause function monomer and carry out atom transfer radical polymerization, directly prepare the segmented copolymer containing antistatic macromolecule function segment, or through further quaternary ammonium reaction or neutralization reaction, prepare the segmented copolymer containing antistatic macromolecule function segment, for as polyacrylic dedicated modified additive, to improve polyacrylic antistatic surface performance.
The existence of modifier molecules of the present invention parent's matrix segment can improve the attachment of properties-correcting agent in polypropylene surface, prevents properties-correcting agent from being rubbed because of material or the erosion action of water comes off, keeps long-acting property and the persistence of antistatic modified effect.
According to, described in this patent, the anti-static function segment of long-acting antistatic polypropylene segmented copolymer has antistatic property. To have the polymer of antistatic property in the selection of this anti-static function segment, comprising: polyacrylate, poly-p styrene sulfonic acid salt, polymaleic acid salt, polystyrene-maleic salt, Polyvinylpyrolidone (PVP) or polyvinyl pyridine quaternary ammonium salt etc. have the polymer segment of antistatic property.The molecular weight of function segment is in the scope of several hundred to several ten thousand, and optimum weight is 1000��8000. The polyacrylate of described antistatic property, poly-p styrene sulfonic acid salt, polymaleic acid salt, polystyrene-maleic salt, Polyvinylpyrolidone (PVP) or polyvinyl pyridine quaternary ammonium salt etc. can directly introduce the two ends of parent's matrix polypropylene segment by atom transfer radical polymerization, or again through reacting acquisition further.
The method of modifying utilizing described long-acting antistatic polypropylene segmented copolymer provided by the invention, comprising: mixed with polypropylene base by described long-acting antistatic polypropylene segmented copolymer by blended mode, what obtain containing long-acting antistatic polypropylene segmented copolymer is material modified; The addition of long-acting antistatic polypropylene segmented copolymer by mass, is the 0.1%��20% of polypropylene base quality.
Further, the addition of long-acting antistatic polypropylene segmented copolymer by mass, is the 1%��10% of polypropylene base quality, it is more preferable to 1%��5%.
The present invention is due to the particular design of structure, antistatic polypropylene segmented copolymer is had amphipathic, polypropylene can be carried out modification by blending method by this multipolymer, can well move when machine-shaping and be adsorbed onto polypropylene material surface, make material modified to there is excellent antistatic property; Meanwhile, due to the existence of polypropylene segment, the more difficult disengaging polypropylene material surface of macromole properties-correcting agent (i.e. this multipolymer), has good long-acting property; In addition, owing to addition is few, major part antistatic modifier (i.e. this multipolymer) migrates to product surface, does not affect the mechanical property of goods.
In a word, parent's matrix polypropylene segment and specific anti-static function segment are combined by the present invention, and the long-acting antistatic polypropylene segmented copolymer of formation, solves problems of the prior art. Technique is simple, and cost is low; Gained is material modified, has good antistatic property, it is possible to avoid the accumulation of static electricity on polypropylene articles surface, thus prevents the problem that produces because of product surface buildup of static electricity or accident; Meanwhile, the sticking power of antistatic polypropylene segmented copolymer improves greatly, it is not easy to come off, and persistence is good so that antistatic property has long-acting property, and don't affects the mechanical property of body material, has huge application prospect and marketable value.
Accompanying drawing explanation
Fig. 1 be according to embodiment 1 obtain material modified in, the surface enrichment result schematic diagram of antistatic polypropylene segmented copolymer, its middle polyline a and b represents respectively: antistatic polypropylene segmented copolymer is at the content on material modified surface and body.
Fig. 2 is the material modified solvent resistant washout test result schematic diagram obtained according to embodiment 2, and its middle polyline a and b represents respectively: before and after etoh solvent washout test, the content of material modified surface segmented copolymer.
Fig. 3 is the relation curve of antistatic modified PP membrane resistance rate and the static inhibitor content obtained according to embodiment 3, and wherein a represents the antistatic copolymer of the present embodiment, and b represents the graft copolymer of polypropylene/polyoxyethylene glycol.
Fig. 4 is the infrared spectrum of the polypropylene block copolymer with anti-static function obtained according to embodiment 4.
Fig. 5 is the hot weightless picture of the polypropylene block copolymer with anti-static function obtained according to embodiment 4.
Embodiment
Following examples are for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
By the cracking in 350 DEG C of nitrogen protections when of 50g isotatic polypropylene, preparation is containing the polypropylene of end double bond, then with hydrogenchloride or hydrogen bromide, the polypropylene of end double bond is carried out addition reaction, obtains the polypropylene of double-ended halogen (chlorine or bromine).
Get the self-control polypropylene of 30g band end chlorine (or end bromine) functionalization, it is dissolved in dimethylbenzene, add CuCl and bipyridine respectively as catalyzer and part, add 50ml vinylformic acid. Induction stirring reaction 12h in 100 DEG C of constant temperature oil baths, cooling, filters. Solid product ethanolic extraction 48h, drying for standby.
Taking 30g polypropylene/polypropylene acid segmented copolymer (without anti-static function) is dissolved in dimethylbenzene, adds the neutralization of sodium hydroxide ethanolic soln, return stirring reaction 1h. Cooling, filters, dry, the obtained polypropylene/polypropylene acid sodium segmented copolymer with anti-static function.
In the segmented copolymer that the present embodiment is obtained, the molecular weight of polypropylene segment is 8000g/mol, and the molecular weight of sodium polyacrylate segment is 6500g/mol.
By material modified to the polypropylene/polypropylene acid sodium segmented copolymer with anti-static function of above-mentioned synthesis and the blended preparation of acrylic resin, the addition with the polypropylene/polypropylene acid sodium segmented copolymer of anti-static function is the material modified of the 1% of acrylic resin weight, it is possible to make the volume specific resistance of modified polypropene and surface resistivity respectively from 5.0 �� 1015�� cm and 2.5 �� 1014�� drops to 5.9 �� 1012�� cm and 1.2 �� 1011����
The present embodiment obtain material modified in, the surface enrichment result schematic diagram of antistatic polypropylene segmented copolymer is as shown in Figure 1, its middle polyline a and b represents respectively: antistatic polypropylene segmented copolymer, in material modified surface and this body burden, shows that antistatic polypropylene segmented copolymer is mainly enriched in material modified surface. This body burden refers to the mean value of antistatic polypropylene segmented copolymer at material modified each layer content.
Embodiment 2
Get the self-control polypropylene of 30g band end chlorine functionalization, it is dissolved in dimethylbenzene, add CuCl and bipyridine respectively as catalyzer and part, add 45g sodium p styrene sulfonate. Induction stirring reaction 12h in 100 DEG C of constant temperature oil baths, cooling, filters. Solid product ethanolic extraction 48h, dry, the polypropylene block copolymer of the obtained poly (sodium 4-styrenesulfonate) segment containing anti-static function.
In the segmented copolymer that the present embodiment is obtained, the molecular weight of polypropylene segment is 4000g/mol, and the molecular weight of poly (sodium 4-styrenesulfonate) segment is 8000g/mol.
By material modified to the polypropylene block copolymer with anti-static function of above-mentioned synthesis and the blended preparation of acrylic resin, the addition with the polypropylene block copolymer of anti-static function is the material modified of the 2% of acrylic resin weight, it is possible to make the volume specific resistance of modified polypropene and surface resistivity respectively from 5.0 �� 1015�� cm and 2.5 �� 1014�� drops to 9.0 �� 1011�� cm and 2.7 �� 1010��. By water or alcohol immersion 48 hours, its anti-static function remains unchanged, and even slightly improves, and embodies material modified long-acting property and persistence.
The material modified solvent resistant washout test result schematic diagram that the present embodiment obtains is as shown in Figure 2, this figure illustrates: before and after ethanol washes away (representing with broken line a and b respectively), the content of material modified surface segmented copolymer is substantially constant, and material modified have antistatic long-acting property.
Embodiment 3
Get the self-control polypropylene of 30g band end chlorine functionalization, it is dissolved in dimethylbenzene, add CuCl and bipyridine respectively as catalyzer and part, add 60g vinylbenzene and 60g maleic anhydride.Induction stirring reaction 12h in 100 DEG C of constant temperature oil baths, cooling, filters. Solid product ethanolic extraction 48h, dry, the obtained polypropylene block copolymer (without anti-static function) containing polystyrene-maleic anhydride segment. By the sodium hydroxide alcoholic solution hydrolysis neutralization of this segmented copolymer, the obtained polypropylene block copolymer (there is anti-static function) containing polystyrene-maleic sodium segment.
In the segmented copolymer that the present embodiment is obtained, the molecular weight of polypropylene segment is 1000g/mol, and the molecular weight of polystyrene-maleic sodium segment is 7500g/mol.
By material modified to the polypropylene block copolymer with anti-static function of above-mentioned synthesis and the blended preparation of acrylic resin, the addition with the polypropylene block copolymer of anti-static function is the material modified of the 4% of acrylic resin weight, it is possible to make the volume specific resistance of modified polypropene and surface resistivity respectively from 5.0 �� 1015�� cm and 2.5 �� 1014�� drops to 1.8 �� 1011�� cm and 6.2 �� 109��. By water or alcohol immersion 48 hours, its antistatic property remains unchanged, and even slightly improves.
The static inhibitor (polypropylene block copolymer containing polystyrene-maleic sodium segment) of the material modified middle interpolation that the application is obtained, compare with the graft copolymer of static inhibitor polypropylene/polyoxyethylene glycol, the relation curve of antistatic modified PP membrane resistance rate and static inhibitor content is as shown in Figure 3, wherein a represents the antistatic copolymer of the present embodiment, b represents the graft copolymer of polypropylene/polyoxyethylene glycol, and Fig. 3 illustrates: the block copolymer-modified successful of antistatic polypropylene of the application's synthesis is better than the graft copolymer of polypropylene/polyoxyethylene glycol.
Embodiment 4
By 45g isotatic polypropylene and 20ml concentrated nitric acid, it is heated to 110 DEG C of backflows, induction stirring, cooling after reaction 16h, filtration, respectively with water, acetone rinsing to pH �� 6, the remaining nitric acid of Ex-all; Gained solid is end carboxyl polypropylene.
30g makes by oneself the heating of end carboxyl polypropylene to be dissolved in pimelinketone, adds 10ml epoxy chloropropane and catalyzer Tetrabutyl amonium bromide 0.7g. Backflow, induction stirring 6h, cooling, filtration. Solid ethanolic extraction 24h, obtains the low-molecular-weight polypropylene of band end chlorine, drying for standby.
Get the self-control polypropylene of 20g band end chlorine functionalization, it is dissolved in dimethylbenzene, add CuCl and bipyridine respectively as catalyzer and part, add 35mlN-vinyl pyrrolidone. Induction stirring reaction 12h in 100 DEG C of constant temperature oil baths, cooling, filters. Solid product ethanolic extraction 48h, dry, the obtained polypropylene, polyethylene base pyrrolidone segmented copolymer with anti-static function.
In the segmented copolymer that the present embodiment is obtained, the molecular weight of polypropylene segment is 2000g/mol, and the molecular weight of Polyvinylpyrolidone (PVP) segment is 6000g/mol. Measuring (collection of illustrative plates is as shown in Figure 4) through infrared quantitative, the content of Polyvinylpyrolidone (PVP) is 85.0%, illustrates that this segmented copolymer has ABA type structure. Fig. 5 is the hot weightless picture of the polypropylene block copolymer with anti-static function obtained according to the present embodiment.
By material modified to the polypropylene block copolymer with anti-static function of above-mentioned synthesis and the blended preparation of acrylic resin, the addition with the polypropylene block copolymer of anti-static function is the material modified of the 5% of acrylic resin weight, it is possible to make the volume specific resistance of modified polypropene and surface resistivity respectively from 5.0 �� 1015�� cm and 2.5 �� 1014�� drops to 2.3 �� 1011�� cm and 1.4 �� 107��.By water or alcohol immersion 48 hours, its antistatic property remains unchanged, and even slightly improves.
Although, above the present invention is described in detail with a general description of the specific embodiments, but on basis of the present invention, it is possible to it being made some modifications or improvements, this will be apparent to those skilled in the art. Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (12)
1. a long-acting antistatic polypropylene segmented copolymer, its general formula is A-B-A, A is anti-static function segment, and B is parent's matrix polypropylene segment; Described anti-static function segment is: polyacrylate, poly-p styrene sulfonic acid salt, polymaleic acid salt, polystyrene-maleic salt, Polyvinylpyrolidone (PVP) or polyvinyl pyridine quaternary ammonium salt; The molecular weight of described parent's matrix polypropylene segment and anti-static function segment is 1000��20000g/mol; The number of repeat unit of described parent's matrix polypropylene segment is 15��400, and the number of repeat unit of described anti-static function segment is 30��750.
2. long-acting antistatic polypropylene segmented copolymer according to claim 1, it is characterised in that, the molecular weight of described parent's matrix polypropylene segment and anti-static function segment is 1000��8000g/mol.
3. the synthetic method of long-acting antistatic polypropylene segmented copolymer described in claim 1 or 2, comprise: cause function monomer polyreaction by parent's matrix polypropylene segment, adopt Transfer Radical Polymerization, using cuprous chloride as catalyzer, take bipyridine as part, temperature of reaction is 50��150 DEG C, and the reaction times is 4��24 hours, prepares long-acting antistatic polypropylene segmented copolymer; Through further quaternary ammonium reaction or with the neutralization reaction of alkali, prepare long-acting antistatic polypropylene segmented copolymer.
4. synthetic method according to claim 3, it is characterised in that, described function monomer is: vinylformic acid, sodium p styrene sulfonate, maleic anhydride, vinylbenzene and maleic anhydride, NVP or vinyl pyridine.
5. synthetic method according to claim 3 or 4, it is characterised in that, described alkali is sodium hydroxide or potassium hydroxide.
6. synthetic method according to claim 3 or 4, it is characterised in that, temperature of reaction is 100 DEG C, and the reaction times is 12 hours.
7. synthetic method according to claim 5, it is characterised in that, temperature of reaction is 100 DEG C, and the reaction times is 12 hours.
8. synthetic method according to claim 3 or 4, it is characterized in that, the synthetic method of described parent's matrix polypropylene segment comprises: by polypropylene by cracking under Pintsch process or concentrated nitric acid effect, and through end group chemical modification, prepare the polypropylene of double-ended halogen.
9. synthetic method according to claim 5, it is characterised in that, the synthetic method of described parent's matrix polypropylene segment comprises: by polypropylene by cracking under Pintsch process or concentrated nitric acid effect, and through end group chemical modification, prepare the polypropylene of double-ended halogen.
10. utilize the method for modifying of long-acting antistatic polypropylene segmented copolymer described in claim 1 or 2, comprising: mixed with polypropylene base by described long-acting antistatic polypropylene segmented copolymer by blended mode, what obtain containing long-acting antistatic polypropylene segmented copolymer is material modified; The addition of long-acting antistatic polypropylene segmented copolymer by mass, is the 0.1%��20% of polypropylene base quality.
11. method of modifying according to claim 10, it is characterised in that, the addition of long-acting antistatic polypropylene segmented copolymer by mass, is the 1%��10% of polypropylene base quality.
12. method of modifying according to claim 11, it is characterised in that, the addition of long-acting antistatic polypropylene segmented copolymer by mass, is the 1%��5% of polypropylene base quality.
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