CN101676309A - Functionalized polypropylene for flexible packages, preparation method thereof and functionalized polypropylene used for preparing flexible packages by the method - Google Patents
Functionalized polypropylene for flexible packages, preparation method thereof and functionalized polypropylene used for preparing flexible packages by the method Download PDFInfo
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Abstract
The invention provides functionalized polypropylene (PP) for flexible packages and a preparation method thereof. The functionalized PP for flexible packages comprises the following components: (a) 30to 70 weight parts of irradiated PP powder; (b) 30 to 70 weight parts of non-irradiated PP powder; and (c) 0.4 to 15 weight parts of polar co-monomer formed by subjecting the irradiated PP powder in component (a) and the non-irradiated PP powder in component (b) to graft copolymerization, and optionally comprising (d) antioxidant and/or lubricant, wherein, the PP powder in component (a) is irradiated in the protective presence of nitrogen with the irradiation source thereof being a cobalt source, the irradiation dose thereof being 20kGy to 60kGy, and the dose rate thereof being 2 to 0.5 kGf/h.The invention intends to prepare PP with higher polarity and improve the print and compound properties of PP films by grafting the polar monomer of glycidyl methacrylate (GMA) and styrene on PP powder on the basis of the pre-irradiation method.
Description
Technical field
The invention belongs to pre-radiotreatment and the application of fusion-grafting technology aspect polymer modification, be specifically related to a kind of soft packaging with functional poly propylene and preparation method thereof and the soft packaging functional poly propylene by the preparation of this method.
Background technology
Polypropylene is one of the thermoplastic macromolecule material of tool development prospect in the world today, and it is widely used in industries such as automobile, household electrical appliances, packing.Before 2000, China's polypropylene needs a large amount of imports, and the degree of self-sufficiency only has an appointment 60%; By 2006, domestic polypropylene consumption reached 9,050,000 tons, and average growth rate per annum has reached 14.1%, and China has become polypropylene country of consumption the biggest in the world at present.
As flexible packing material, the consumption of polypropylene film is only second to polyethylene, accounts for second; Processing mode according to polypropylene film can be divided into IPP (blown film), CPP (casting films), BOPP (biaxial stretching film).
Polypropylene (PP) is mainly used to make the multilayer complex films of high barrier in the soft packaging field, can be used as the skin of composite membrane or the material of internal layer; The form of outer (printed layers) generally is BOPP; CPP with heat sealability then mainly is used as the internal layer of composite membrane, and this composite membrane is generally as making high-temperature retort bag.
Through the development of recent two decades, China CPP and BOPP have developed into the industry with certain industrial scale and production level.According to statistics, family surplus the existing CPP manufacturing enterprise 30 of China, surplus the production line 50 (annual production more than 6000 tons about 10), 250,000 tons of overall throughputs; More than 60 families (output is in 13 families of the enterprise more than 4.5 ten thousand tons) of BOPP manufacturing enterprise, 1,690,000 tons of overall throughputs.
According to the requirement of different application occasion, the form of high-temperature retort bag mainly contains two layers of compound, three layers of compound, four layers of form such as compound on the China market.Two layers of compound form have: BOPA/CPP, PET/CPP; Three layers of compound have: PET/Al/CPP, BOPA/Al/CPP, PET/BOPA/CPP, BOPA/PVDC/CPP, PET/PVDC/CPP; Four layers compound: PET/BOPA/Al/CPP, PET/Al/BOPA/CPP.Wherein PVDC is a polyvinylidene chloride resin.In the structure of light packing bag, the structure of Al/CPP can use VM-CPP (cast polypropylene aluminium plating film) to replace sometimes, because compare with foil laminated film, VM-CPP has that aluminium coated is relatively thin, material becomes low, snappiness good, can avoid the aluminium foil bend fracture and the characteristics such as barrier property reduction that cause.Therefore VM-CPP has been substituted the market of the compound flexible packaging of aluminium foil greatly.
People find when CPP or VM-CPP prepare flexible packing material using, because CPP resin polarity is very low, with other material (as PA, PET) compound tense, the peel strength of polypropylene film and PA, PET film is lower, causes high-temperature retort bag CPP film generation absciss layer phenomenon when retort sterilization; Aluminium coated takes place the VM-CPP of light packing bag easily shifts.In addition, the organic solvent in binding agent or the printing ink, particularly toluene are easy to be absorbed and the desorption difficulty by polypropylene material, are easy to cause that toluene is residual in the final packaging goods exceeds standard, and the higher PET film of polarity to the adsorptive capacity of toluene seldom.
Polypropylene is carried out the pre-irradiation grafting polar monomer, can improve the polarity of polypropylene film, and then improve its printing, composite performance as flexible packing material.Printing packaging field at home, preparation and the applied research of high polarity PP yet there are no report.
At present existing Chinese patent application 200610016707.7 has been reported a kind of preparation method of functional poly propylene material, the modified polypropene of this patent application preparation can be used as the tack coat of polypropylene and metal, pottery, glass, the expanding material of polypropylene/polar polymer alloy.
But, has good combined strength bination for PA, PET film in the market, the VM-CPP that makes high-temperature retort bag CPP film when retort sterilization be difficult for generation absciss layer phenomenon or light packing bag is not easy to take place aluminium coated transfer, low solvent residue, and have higher printing and composite performance, but and meet the relevant contact food of China and European Union and great demand is still arranged with the modified polypropene of the relevant laws and regulations of wrapping material.
Summary of the invention
For this reason, one aspect of the present invention provides a kind of soft packaging functional poly propylene.
Another aspect of the present invention provides a kind of soft packaging polyacrylic preparation method of functionalization.
Another aspect of the present invention provides a kind of soft packaging functional poly propylene by above-mentioned preparation method's preparation.
The invention provides a kind of soft packaging functional poly propylene, comprising:
(a) polypropylene powder through irradiation of 30～70 weight parts;
(b) polypropylene powder without irradiation of 30～70 weight parts;
(c) 0.4～15 weight part with described (a) through the polypropylene powder of irradiation and described (b) without the polarity of the polypropylene powder graft copolymerization of irradiation monomer altogether;
(d) optional oxidation inhibitor and/or the lubricant of comprising;
Wherein, described (a) carries out irradiation through the polypropylene powder of irradiation under nitrogen protection, and used source of radiation is the cobalt source, and radiation dose is 20～60kGy, and dose rate is 2～0.5kGy/h.
Preferably, the polarity of described (c) graft copolymerization monomer altogether is at least a polar monomer and at least a non-polar monomer, more preferably glycidyl methacrylate and cinnamic mixture, adding proportion be described (a) and (b) two kinds of polypropylene gross weights 0.6～10%, glycidyl methacrylate and cinnamic weight blending ratio that the polarity of wherein said (c) graft copolymerization is total in the monomer are 1: 1～1: 5, and described soft packaging further comprises oxidation inhibitor and/or lubricant with functional poly propylene.
Preferably, described (a) is 40: 60～60: 40 through polypropylene and described (b) of irradiation without the polyacrylic part by weight of radiating, and described soft packaging further comprises oxidation inhibitor and/or lubricant with functional poly propylene.
Preferably, described radiation dose is 30～50kGy, and dose rate is 1.5～0.8kGy/h, and wherein said oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, and described lubricant is selected from calcium stearate, Magnesium Stearate.
Preferably, described radiation dose is 35～45kGy, and dose rate is 1.0kGy/h, and the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
The invention provides a kind of soft packaging polyacrylic preparation method of functionalization, comprising:
Step a: polypropylene powder is carried out irradiation under nitrogen protection, used source of radiation is the cobalt source, and radiation dose is 20～60kGy, and dose rate is 2～0.5kGy/h;
Step b: the described polypropylene powder after step a radiation was placed 6～48 hours; And
Step c: will be after step b places through the described polypropylene powder of irradiation with without the radiating polypropylene powder with polarity altogether monomeric grafted monomer carry out the fusion-grafting modification, wherein optional interpolation oxidation inhibitor and/or lubricant,
Wherein, through the described polypropylene powder of irradiation be 30～70 weight parts, without the described polypropylene powder of radiating be 30～70 weight parts, described polarity altogether monomer be 0.4～15 weight part.
Preferably, the polarity that described grafted monomer is used monomer altogether is at least a polar monomer and at least a non-polar monomer, more preferably glycidyl methacrylate and cinnamic mixture, wherein said glycidyl methacrylate and cinnamic weight blending ratio are 1: 1～1: 5.
Preferably, the described polypropylene powder after step a radiation was placed 12～36 hours.
More preferably, the described polypropylene powder after step a radiation was placed 24 hours.
Preferably, is 40: 60～60: 40 through the described polypropylene powder of irradiation with weight ratio without the described polypropylene powder of radiating, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
Preferably, described radiation dose is 30～50kGy, dose rate is 1.5～0.8kGy/h, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
More preferably, described radiation dose is 35～45kGy, dose rate is 1.0kGy/h, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
The present invention also provides a kind of soft packaging functional poly propylene, and it is by above-mentioned method preparation.
Soft packaging according to the present invention has following advantage with functional poly propylene:
(1) because graft copolymerization monomer glycidyl methacrylate has higher sterically hindered, if therefore when grafting, do not add common monomer styrene, the percentage of grafting of glycidyl methacrylate can be very low so, influence graft effect, cause more monomer residue, cause a hidden trouble for food safety.Therefore the present invention selects the common monomer of vinylbenzene as glycidyl methacrylate for use, can greatly improve the percentage of grafting of polar monomer glycidyl methacrylate.
(2) the used source of radiation of the present invention is the cobalt source, radiation dose is 20～60kGy, be preferably 30～50kGy, 35～45kGy more preferably, dose rate is 2～0.5kGy/h, is preferably 1.5～0.8kGy/h, most preferably be 1.0kGy/h, radiant ratio is low, and radiated time is long, has guaranteed the homogeneity of the free radical of generation effectively.And irradiation has guaranteed the life-span of free radical under nitrogen protection, prevent the degraded that air causes polypropylene effectively.
(3) polypropylene of the present invention after with radiation placed 6～48 hours, preferably placed 12～36 hours, most preferably placed and carried out the fusion-grafting modification after 24 hours again.The purpose of placing is to make free radical to move (radical transfer) on acrylic resin, makes the distribution of free radical more even, and then makes graft product to distribute more equably.It is 30: 70～70: 30 that the present invention selects best pre-radiation polypropylene and the polyacrylic ratio of radiation not for use, is preferably 40: 60～60: 40, and this ratio is beneficial to the uniform distribution of graft product, also is beneficial to the mechanical property of improving the finished product.
(4) the present invention is prepared modified polypropene is used for food flexible packing material, and the preparation composite plastic film can improve polyacrylic printing and composite performance.And but this modified polypropene also meets the relevant laws and regulations of the relevant contact food of China and European Union with wrapping material.
Embodiment
Below with reference to embodiment to a kind of soft packaging according to the present invention with functional poly propylene and preparation method thereof; with and performance test specifically describe; those skilled in the art should understand; following specific descriptions are for the ease of understanding the present invention, not being used for limiting protection scope of the present invention.
In the application's a embodiment, a kind of soft packaging functional poly propylene is disclosed.
In another embodiment of the application, a kind of soft packaging polyacrylic preparation method of functionalization is disclosed.
In another embodiment of the application, a kind of soft packaging functional poly propylene by above-mentioned preparation method's preparation is disclosed.
In a specific embodiment of the present invention, a kind of soft packaging functional poly propylene is provided, comprising:
(a) polypropylene powder through irradiation of 30～70 weight parts;
(b) polypropylene powder without irradiation of 30～70 weight parts;
(c) 0.4～15 weight part with described (a) through the polypropylene powder of irradiation and described (b) without the polarity of the polypropylene powder graft copolymerization of irradiation monomer altogether;
(d) optional oxidation inhibitor and/or the lubricant of comprising;
Wherein, described (a) carries out irradiation through the polypropylene powder of irradiation under nitrogen protection, and used source of radiation is the cobalt source, and radiation dose is 20～60kGy, and dose rate is 2～0.5kGy/h.
In a preferred embodiment, the polarity of described (c) graft copolymerization monomer altogether is at least a polar monomer and at least a non-polar monomer, more preferably glycidyl methacrylate and cinnamic mixture, adding proportion be described (a) and (b) two kinds of polypropylene gross weights 0.6～10%, glycidyl methacrylate and cinnamic weight blending ratio that the polarity of wherein said (c) graft copolymerization is total in the monomer are 1: 1～1: 5, and described soft packaging further comprises oxidation inhibitor and/or lubricant with functional poly propylene.
In another preferred embodiment, described (a) is 40: 60～60: 40 through polypropylene and described (b) of irradiation without the polyacrylic part by weight of radiating, and described soft packaging further comprises oxidation inhibitor and/or lubricant with functional poly propylene.
In a preferred embodiment, described radiation dose is 30～50kGy, and dose rate is 1.5～0.8kGy/h, and wherein said oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, and described lubricant is selected from calcium stearate, Magnesium Stearate.
In a more preferred embodiment, described radiation dose is 35～45kGy, and dose rate is 1.0kGy/h, and the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
In another specific embodiment of the present invention, a kind of soft packaging polyacrylic preparation method of functionalization is provided, comprising:
Step a: polypropylene powder is carried out irradiation under nitrogen protection, used source of radiation is the cobalt source, and radiation dose is 20～60kGy, and dose rate is 2～0.5kGy/h;
Step b: the described polypropylene powder after step a radiation was placed 6～48 hours;
And
Step c: will be after step b places through the described polypropylene powder of irradiation with without the radiating polypropylene powder with polarity altogether monomeric grafted monomer carry out the fusion-grafting modification, wherein optional interpolation oxidation inhibitor and/or lubricant,
Wherein, through the described polypropylene powder of irradiation be 30～70 weight parts, without the described polypropylene powder of radiating be 30～70 weight parts, described polarity altogether monomer be 0.4～15 weight part.
In a preferred embodiment, the polarity that described grafted monomer is used monomer altogether is at least a polar monomer and at least a non-polar monomer, more preferably glycidyl methacrylate and cinnamic mixture, wherein said glycidyl methacrylate and cinnamic weight blending ratio are 1: 1～1: 5.
In another preferred embodiment, the described polypropylene powder after step a radiation was placed 12～36 hours.
In a more preferred embodiment, the described polypropylene powder after step a radiation was placed 24 hours.
In a preferred embodiment, is 40: 60～60: 40 through the described polypropylene powder of irradiation with weight ratio without the described polypropylene powder of radiating, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
In a preferred embodiment, described radiation dose is 30～50kGy, dose rate is 1.5～0.8kGy/h, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
In a more preferred embodiment, described radiation dose is 35～45kGy, dose rate is 1.0kGy/h, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
In another specific embodiment of the present invention, a kind of soft packaging functional poly propylene also is provided, it is by above-mentioned method preparation.
Illustrate the specific embodiment of the present invention below.
The preparation of embodiment 1 functional poly propylene sample
Step 1: (No. 2 Petro-Chemical Plant, Tianjin Petro-Chemical Corporation, trade mark TC-1) is placed in the plastic tank of sealing with polypropylene (PP) powder, purges 1 hour with the flow of high pure nitrogen with 100L/min, removes the oxygen in the material, then sealed storage.
Step 2: the PP powder of above-mentioned deoxidation is being carried out gamma-ray irradiation under the nitrogen protection, under 1.0kGy/ hour dose rate, used source of radiation is the cobalt source, and (always) irradiation dose is 40kGy, wherein (always) radiation dose=dose rate * radiated time.
Step 3: after the PP powder behind the irradiation placed 24 hours, under nitrogen protection, according to table 1 proportioning, with other oxidation inhibitor, lubricant, polar monomer (glycidyl methacrylate, below represent), monomer (vinylbenzene) blend 3～10min altogether with GMA.
Each proportioning raw materials of table 1 preparation MODIFIED PP
Step 4: above-mentioned raw material through blend is melt extruded on twin screw extruder, and extruder temperature control sees Table 2, and wherein twin screw extruder is a parallel dual-screw compounding forcing machine, model C TE35, and the mechanical company limited of times Long Keya of section (Nanjing) produces.So just obtained the functional poly propylene resin.
Table 2 MODIFIED PP melt extrude condition
With above-mentioned functions acrylic resin injection batten in injector (B.ZT-II, Shanghai Sanhuai Coating Machine Co., Ltd produces), measure its mechanical property then.
With reference to People's Republic of China's light industry standard or CNS QB1956-94 (polypropylene blown film), GB/T 10003-1996 (coventional type BiOriented Polypropylene Films), GB/T 16958-1997 (packaging biaxially oriented polyester film), GB/T12026-2000 (heat sealing type biaxial-tension polypropylene film), QB/T 1125-2000 (not stretching polyethylene, polypropylene film) mechanical property of the acrylic resin of graft modification is detected, the results are shown in Table shown in 3.
The physicals test result of table 3 MODIFIED PP
As shown in Table 3, PP behind the pre-irradiation grafting compares with unmodified PP, indexs such as stretching yield stress, tensile break stress, flexural strength, cantilever beam impact strength descend to some extent, and this is because due to polypropylene molecule is degraded in irradiation and polypropylene fusion graft process.
Sample 1 (being the raw materials melt grafting with the PP through irradiation all), its every mechanical property all has remarkable decline, illustrates that irradiation can bring out polyacrylic degraded, makes its structure and performance that some changes correspondingly take place.Compare with No. 0 sample (unmodified PP), No. 1 sample stretching yield stress decline 9.3%, tensile break stress decline 59%, flexural strength decline 11%, cantilever beam impact strength descend 74%.
Add the pp material of part without irradiation, the mechanical property of the modified resin of preparing has preferably to be improved.Sample 2 (respectively be 1kg through the PP of irradiation with PP without irradiation, and vinylbenzene respectively is 10g with GMA) is compared with sample 0, and its stretching yield stress descends 4%, tensile break stress descends 25%, flexural strength descends 4.5%, cantilever beam impact strength decline 35%; Compare with No. 1 sample, the mechanical property of sample 2 has had preferably to be improved.
Polar monomer consumption in the sample 3 (respectively be 1kg through the PP of irradiation with PP without irradiation, and vinylbenzene and GMA respectively are 20g) is sample 1 and 2 two times, and the indexs such as tensile strength of sample 3 materials are substantially close with 2 samples.Explanation adds the mechanical property that irradiated polypropylene raw material not can obviously improve graft product when fusion-grafting.
Sample 4 is (through the polypropylene 0.8kg of irradiation, polypropylene 1.2kg without irradiation, vinylbenzene 40g, GMA 160g) added more GMA polar monomer in, in order to increase its percentage of grafting, also introduced more styrene co-monomer, and the consumption of unmodified polypropylene raw material is higher than the irradiated polypropylene consumption, the mechanical property of the modification sample that obtains is best.The heat-drawn wire of the acrylic resin behind pre-irradiation grafting improves 2～4 ℃ with respect to sample 0 (not grafting sample).This is because introduce the polarity segment in polypropylene after, these polarity segments play the heterogeneous nucleation effect, have increased the physical crosslinking point of polypropylene molecule, makes thermostability improve.The above-mentioned functional poly propylene resin that obtains is prepared casting films on the small-sized casting machine in laboratory, carry out following test then: (1) measures the contact angle of film and water with reference to ANSI/ASTM D5725-1997; (2) compound with pre-coating film (scotch tape), with reference to GB 8808-88 (soft composite plastics material stripping test method), peel off experiment, measure the size of its average peeling force; (3),, detect after the raising of PP polarity the in press improvement situation of application performance by detecting on the PP material ink marks by the sticking degree down of adhesive tape with reference to GB/T 13217.7-91 (check of intaglio plate ink used for plastic method of inspection attachment fastness).
Contact angle can characterize the polarity of acrylic resin indirectly, and after the pre-irradiation grafting modification, the contact angle of acrylic resin and water is shown in Table 4.
The contact angle test result of table 4 MODIFIED PP and water
Find out that by table 4 the contact angle of the polypropylene of graft modification and water is not 108.7 °, show that it is non-wetted to polar printing ink and binding agent basically, so its printing composite performance is relatively poor.PP is all little than unmodified PP with the contact angle of water after the modification, illustrate that the degree that water droplet sprawls is better than No. 0 sample on the PP material, the modified effect of sample 3,4,5 is more obvious, the MODIFIED PP resin of sample 4 and the contact angle of water only are 87.6 °, show that it is better to the wettability of polar printing ink and binding agent, have good printing composite performance, and the mechanical property of sample 4 descends also seldom.
With reference to GB8808-88 (soft composite plastics material stripping test method), the laminated film of preparing has been carried out stripping test, measure the size of the average peeling force of laminated film, the results are shown in Table shown in 5.
Table 6PP and wide scotch tape compound peel test force result
As shown in Table 6, the stripping strength of unmodified PP composite membrane has only 2.5 newton, and the peeling force of the polypropylene composite film behind pre-irradiation grafting can improve 16～68%.
Printability test: with reference to GB/T 13217.7-91 (check of intaglio plate ink used for plastic method of inspection attachment fastness), by the degree under ink marks is glued by adhesive tape on the detection PP material, the improvement situation of application performance in press after detecting PP polarity and improving, measurement result is shown in Table 7.
The printing ink attachment fastness test result of table 7 MODIFIED PP
As shown in Table 8, compare with unmodified PP, the PP resin is multiplied (1.1～3.8 times) for the attachment fastness of printing ink after the modification, and is strengthened successively by sample 1 to sample 5.Illustrate that the polarity of PP resin improves a lot after the modification, very big for the printing performance contribution that improves film.
Have significantly differently based on the soft packaging of the present invention of the foregoing description preparation with the polyacrylic preparation method of functionalization and modified polypropene in the patent application formerly, and have following advantage, be in particular in following several aspect:
(1) raw material difference.The used grafted monomer of the present invention is for being total to monomer, be glycidyl methacrylate and cinnamic mixture, blending ratio is 1: 1～1: 5, adopt vinylbenzene as being total to the percentage of grafting that monomeric purpose is to improve the polar monomer glycidyl methacrylate, reduce the glycidyl methacrylate space steric effect.And patent application formerly only selects for use a kind of monomer as grafted monomer.
(2) radiation treatment protocols difference.The used source of radiation of the present invention is the cobalt source, radiation dose is 20～60kGy, be preferably 30～50kGy, 35～45kGy more preferably, dose rate is 2～0.5kGy/h, is preferably 1.5～0.8kGy/h, most preferably be 1.0kGy/h, radiant ratio is low, and radiated time is long, has guaranteed the homogeneity of the free radical of generation effectively.And irradiation prevents that air from causing degraded to polypropylene under nitrogen protection.And patent application formerly is to adopt electron beam to carry out pre-radiotreatment under air conditions.
(3) preparation technology's difference.The polypropylene of the present invention after with radiation placed 6～48 hours, preferably placed 12～36 hours, most preferably placed and carried out the fusion-grafting modification after 24 hours again.The purpose of placing is to make free radical to move (transfer) at acrylic resin, and the distribution of free radical is more even, and then makes graft product also compare uniform distribution.It is 30: 70～70: 30 that the present invention selects best pre-radiation polypropylene and the polyacrylic ratio of radiation not for use, is preferably 40: 60～60: 40, and this ratio helps the uniform distribution of graft product
(4) the Application Areas difference of modified polypropene.The prepared modified polypropene of the present invention is used for food flexible packing material, the preparation composite plastic film, and purpose is to improve polyacrylic printing and composite performance.And but this modified polypropene meets the relevant laws and regulations of the relevant contact food of China and European Union with wrapping material.
In addition, the polarity of adding in embodiment 1 step (3) monomer altogether also can comprise the 3rd monomer, methacrylic ester, acrylate, acrylic or methacrylic acid isopolarity monomer as other types, for example, butyl methacrylate, hydroxyethyl methylacrylate, methacrylic acid-2-ethylhexyl, methacrylic acid.And, utilize the modified polypropene that comprises above-mentioned the 3rd monomer preparation also to have good composite performance.
Among the application, the implication of term " optional " is to have the technical characterictic or the key element that also can not have thereafter, and this feature or key element are optional.
Those skilled in the art should understand that above preferred embodiment just specifies of the present invention, is not construed as limiting the invention.Can carry out multiple improvement to it as required, combination, subgroup is closed and conversion, all improvement, combination, subgroup is closed, conversion and equivalence are replaced and all to be fallen within the scope of appended claim.
Claims (13)
1. soft packaging functional poly propylene comprises:
(a) polypropylene powder through irradiation of 30～70 weight parts;
(b) polypropylene powder without irradiation of 30～70 weight parts;
(c) 0.4～15 weight part with described (a) polypropylene powder through irradiation
And described (b) is without the common monomer of the polarity of the polypropylene powder graft copolymerization of irradiation;
(d) optional oxidation inhibitor and/or the lubricant of comprising;
Wherein, described (a) carries out irradiation through the polypropylene powder of irradiation under nitrogen protection, and used source of radiation is the cobalt source, and radiation dose is 20～60kGy, and dose rate is 2～0.5kGy/h.
2. soft packaging functional poly propylene according to claim 1, wherein, the polarity of described (c) graft copolymerization monomer altogether is at least a polar monomer and at least a non-polar monomer, be preferably glycidyl methacrylate and cinnamic mixture, adding proportion be described (a) and (b) two kinds of polypropylene gross weights 0.6～10%
Glycidyl methacrylate and cinnamic weight blending ratio that the polarity of wherein said (c) graft copolymerization is total in the monomer are 1: 1～1: 5, and described soft packaging further comprises oxidation inhibitor and/or lubricant with functional poly propylene.
3. soft packaging functional poly propylene according to claim 1, wherein, described (a) is 40: 60～60: 40 through polypropylene and described (b) of irradiation without the polyacrylic part by weight of radiating, and described soft packaging further comprises oxidation inhibitor and/or lubricant with functional poly propylene.
4. according to each described soft packaging functional poly propylene in the claim 1～3, wherein, described radiation dose is 30～50kGy, dose rate is 1.5～0.8kGy/h, wherein said oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, and described lubricant is selected from calcium stearate, Magnesium Stearate.
5. according to each described soft packaging functional poly propylene in the claim 1～3, wherein, described radiation dose is 35～45kGy, dose rate is 1.0kGy/h, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
6. a soft packaging comprises with the polyacrylic preparation method of functionalization:
Step a: polypropylene powder is carried out irradiation under nitrogen protection, used source of radiation is the cobalt source, and radiation dose is 20～60kGy, and dose rate is 2～0.5kGy/h; Step b: the described polypropylene powder after step a radiation was placed 6～48 hours; And
Step c: will be after step b places through the described polypropylene powder of irradiation with without the radiating polypropylene powder with polarity altogether monomeric grafted monomer carry out the fusion-grafting modification, wherein optional interpolation oxidation inhibitor and/or lubricant,
Wherein, through the described polypropylene powder of irradiation be 30～70 weight parts, without the described polypropylene powder of radiating be 30～70 weight parts, described polarity altogether monomer be 0.4～15 weight part.
7. preparation method according to claim 6, wherein, the polarity that described grafted monomer is used monomer altogether is at least a polar monomer and at least a non-polar monomer, be preferably glycidyl methacrylate and cinnamic mixture, wherein said glycidyl methacrylate and cinnamic weight blending ratio are 1: 1～1: 5.
8. preparation method according to claim 6 wherein, places the described polypropylene powder after step a radiation 12～36 hours.
9. preparation method according to claim 6 wherein, places the described polypropylene after the radiation 24 hours.
10. according to each described preparation method in the claim 6～9, wherein, is 40: 60～60: 40 through the described polypropylene powder of irradiation with weight ratio without the described polypropylene powder of radiating, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
11. according to each described preparation method in the claim 6～9, wherein, described radiation dose is 30～50kGy, dose rate is 1.5～0.8kGy/h, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, and the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
12. according to each described preparation method in the claim 6～9, wherein, described radiation dose is 35～45kGy, dose rate is 1.0kGy/h, described oxidation inhibitor is selected from 1010 oxidation inhibitor, 168 oxidation inhibitor or its mixture, described lubricant is selected from calcium stearate, Magnesium Stearate, and the amount of described oxidation inhibitor is the 0.05-3% of two kinds of polypropylene gross weights, and the amount of described lubricant is the 0.05-3% of two kinds of polypropylene gross weights.
13. a soft packaging functional poly propylene, it is by each described method preparation in the claim 6～12.
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| CN102964684A (en) * | 2012-12-03 | 2013-03-13 | 北京印刷学院 | Modified auxiliary capable of improving printing compound performance of polypropylene film, preparation method and application |
| CN102964683A (en) * | 2012-12-03 | 2013-03-13 | 北京印刷学院 | Polypropylene modified master batch and low-residual solvent polypropylene flexible package thin film |
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| CN1817943A (en) * | 2006-01-16 | 2006-08-16 | 大连理工大学 | High-polymer material functional modification |
| CN100497463C (en) * | 2006-03-24 | 2009-06-10 | 中国科学院长春应用化学研究所 | Process for preparing functional poly propylene material |
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