CN114736462B - Ultralow-temperature heat sealing material for polypropylene and preparation method and application thereof - Google Patents

Ultralow-temperature heat sealing material for polypropylene and preparation method and application thereof Download PDF

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CN114736462B
CN114736462B CN202210545107.9A CN202210545107A CN114736462B CN 114736462 B CN114736462 B CN 114736462B CN 202210545107 A CN202210545107 A CN 202210545107A CN 114736462 B CN114736462 B CN 114736462B
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polypropylene
heat sealing
copolymer
heat
ethylene
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CN114736462A (en
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方文彬
方晨
徐董
刘正训
薛圣光
郑国星
张庆
王海伟
方鑫鑫
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Wenzhou Gettel Plastic Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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Abstract

The application provides an ultralow temperature heat sealing material for polypropylene, and a preparation method and application thereof, and belongs to the technical field of compositions taking propylene copolymers as base materials. Is prepared from copolypropylene, poly fatty acid, low-density polyethylene, elastomer, vulcanizing agent and antioxidant through sulfurizing, extruding and granulating. The heat sealing material is used for biaxially oriented polypropylene films, heat-shrinkable polypropylene films and polypropylene casting films, and has the advantages of low heat sealing temperature, wide temperature range, high heat bonding strength, good light transmittance and the like.

Description

Ultralow-temperature heat sealing material for polypropylene and preparation method and application thereof
Technical Field
The application relates to an ultralow temperature heat sealing material for polypropylene, a preparation method and application thereof, belonging to the technical field of compositions taking propylene copolymer as a base material.
Background
The polypropylene film is an important product in the packaging field, has the advantages of light weight, transparency, no toxicity, moisture resistance, high mechanical strength and the like, is widely used for packaging products such as food, medicine, cigarettes and the like, and is widely used as a base material of a composite film. When a common BOPP (biaxially oriented polypropylene film) is heated, molecules are in unorientation and molecular chains are contracted, so that the vicinity of a heated area is thinned and broken, the biaxially oriented polypropylene film does not have heat sealing performance, cannot be used as a film heat sealing layer, and the BOPP and the heat sealing layer are required to be compounded to form a heat-sealable packaging film.
The following properties are required for the heat seal as BOPP film heat seal:
(1) the heat-sealing temperature of the heat-sealing material is obviously lower than that of the BOPP substrate;
(2) high heat seal strength and hot tack strength;
(3) transparency is the same as or higher than that of the base BOPP;
(4) is suitable for high-speed automatic production, and can not adhere in production.
The BOPP film heat-sealing material generally adopts copolymerized polypropylene synthesized by spherical Ziegler-Natta catalysis, and the melting point and crystallinity of the material can be reduced by copolymerization, so that the heat-sealing performance, optical performance and low-temperature impact resistance of the material are improved to a certain extent. The following two problems still remain:
on the one hand, the heat sealing temperature is high, and the heat sealing performance is poor. The comonomer is unevenly dispersed and can generate continuous discharge phenomenon, a polyethylene chain with strong crystallization capability is generated, so that the haze is increased, at the moment, the introduction of the comonomer can not reduce the sealing temperature of the heat sealing material, and the currently produced ternary random copolymer polypropylene can be divided into five grades of extremely ultralow temperature sealing temperature (below 100 ℃), ultralow temperature sealing temperature (100-108 ℃), medium sealing temperature (115-118 ℃), general heat sealing temperature (l 20-130 ℃) and high heat sealing temperature (l 30 ℃) according to the heat sealing temperature, and the demand of the extremely ultralow temperature heat sealing material is rapidly increased along with the development of high-speed automatic packaging technology. The comonomer introduced in the traditional multicomponent copolymerization process has a certain bottleneck for reducing the heat sealing temperature of the material, and cannot fully meet the market demand.
On the other hand, heat-sealing materials cause roll sticking during film processing. The blending of the low molecular weight component is easy to stick to the roller, the production cannot be carried out, and the low molecular weight component is easy to damage the smooth surface of the product, and the glossiness is influenced, so that serious product defects are caused.
Disclosure of Invention
In view of the above, the application firstly provides an ultralow temperature heat sealing material for polypropylene, which takes a poly fatty acid and polyolefin resin compound as main components, effectively improves the heat sealing performance of the material, and endows the material with ultralow initial heat sealing temperature and wide heat sealing temperature range; meanwhile, the introduction of the biomass poly fatty acid can effectively improve the environmental protection property of the product.
Specifically, the application is realized by the following scheme:
the ultralow temperature heat sealing material for polypropylene is prepared by vulcanizing, extruding and granulating the following components in proportion:
when the formula is adopted, the poly-bio-oil has both a cross-linked fatty chain and a carboxyl, and the heat sealing performance of the material is effectively improved by matching with the copolypropylene, the elastomer winds the active components in the structure of the poly-bio-oil with the copolypropylene, and amorphous molecules of components such as low-density polyethylene are grafted onto the polypropylene chain under the matching actions of vulcanizing agent, antioxidant and the like, so that the formed heat sealing material has better heat sealing performance: the initial heat-sealing temperature is below 75 ℃; the heat sealing temperature of the material is 70-145 ℃, so that the requirements of different application scenes can be met; the material has high hot adhesion strength: 13N/15mm, can meet the packaging requirement of high speed (800 bags/min of high speed cigarette packaging machine); the material can meet the high-speed packaging process of powder and liquid, and has excellent inclusion heat sealability; the light transmittance of the material is more than 90%, and the transparency is high.
Further, as preferable:
the polypropylene copolymer is one or a mixture of two copolymers such as ethylene propylene copolymer, butene propylene copolymer and the like and one or more ethylene propylene butene terpolymer, the melt index (MI, 230 ℃/2.16 kg) of the polypropylene copolymer is 2-7 g/10min, and the Melting Point (MP) is 123-140 ℃. The copolymer polypropylene adopts the binary copolymer or the ternary copolymer, and provides an effective structural basis for entanglement of the elastomer and grafting of amorphous molecules.
The poly fatty acid is obtained by initiating polymerization of unsaturated fatty acid through azodiisobutyronitrile, wherein the unsaturated fatty acid is one or a composition of more than two of oleic acid, decenoic acid, myrcenoic acid, myristoleic acid, erucic acid, linoleic acid, decadienoic acid, linolenic acid and the like. The unsaturated fatty acid is brought into a polymerized structure, the fatty chain and carboxyl structure of the polymerized fatty acid are endowed, and the formed polymerized fatty acid has the advantages of reproducibility, environmental protection and cost control.
The density of the low-density polyethylene is 0.910-0.925 g/cm 3 Is also referred to as a non-linear low density polyethylene) and has a density of 0.918 to 0.940g/cm 3 Either or a mixture of both of the linear low density polyethylenes of (a) having a melt index (MI, 230 ℃ C./2.16 kg) of 2 to 7g/10min and a Melting Point (MP) of 105 to 127 ℃. The low density polyethylene of the two structures has abundant amorphous molecules, and when grafted on the polypropylene copolymer chains, the order of the polypropylene chains is effectively destroyed.
The elastomer is ethylene propylene diene monomer (EPDM, density is 0.83-0.87 g/cm) 3 Ethylene content 55-63%), ethylene-octene copolymer (POE, density 0.85-0.91 g/cm 3 MI,230 ℃/2.16Kg of 2-7 g/10 min), ethylene-hexene copolymer (POE, density 0.86-0.90 g/cm 3 MI,230 ℃/2.16Kg of 3-7 g/10 min), ethylene-butene copolymer (POE, density 0.86-0.90 g/cm 3 MI 230 ℃/2.16Kg is 3-7 g/10 min), ethylene-vinyl acetate copolymer (EVA, MI 230 ℃/2.16Kg is 4-20 g/10min, VA content is 8-45%), ethylene-acrylic acid copolymer (EAA, density is 0.928-0.94 g/cm) 3 MI,230 ℃/2.16Kg of 2-20 g/10 min), ethylene-butyl acrylate copolymer (EBA, density 0.924-0.94 g/cm 3 MI,230 ℃/2.16Kg of 2-20 g/10 min), ethylene-methyl acrylate copolymer (EMA, density 0.93-0.96 g/cm 3 MI,230 ℃/2.16Kg is 2 to the upper15g/10 min), ethylene-ethyl acrylate copolymer (EEA, density 0.93-0.94 g/cm 3 MI,230 ℃/2.16Kg of 3-15 g/10 min), polyethylene sodium acrylate (Surlyn, density 0.94-0.97 g/cm 3 MI,230 ℃/2.16Kg of 1-8 g/10 min), styrene-butadiene block copolymer (SBS, density 0.89-0.95 g/cm) 3 MI,230 ℃/2.16Kg of 2-10 g/10 min), pentylene block copolymer (SIS, density 0.918-0.93 g/cm) 3 MI,230 ℃/2.16Kg is 2-15 g/10 min). The special structure of the elastomer has active component with long amorphous alkyl chain, and can be entangled with the copolymer polypropylene molecule more effectively.
The vulcanizing agent is one or more of benzoyl peroxide, dicumyl peroxide, benzoic peroxide, methyl ethyl ketone peroxide, neodecanoic peroxide and tert-butyl peroxypivalate. The vulcanizing agent ensures that the components of the heat sealing material can be stably and dynamically vulcanized.
The antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076), 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (CA), 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (330) Butyl Hydroxy Anisole (BHA), dibutyl hydroxy toluene (BHT), propyl Gallate (PG) and tert-butyl hydroquinone (TBHQ). The use of the above antioxidants gives the material a smoother surface and a durable service life.
The second aspect of the present application is to provide a method for preparing the heat-sealing material, comprising the steps of:
(1) Poly fatty acid synthesis: adding unsaturated fatty acid and azodiisobutyronitrile according to the mass ratio of 100:1-3, heating to 130-230 ℃, stirring and polymerizing for 10-24 h, and then distilling under reduced pressure for 1-6 h to obtain poly fatty acid;
(2) And (3) preparing a heat sealing material: adding the poly fatty acid, the copolymerized polypropylene, the low-density polyethylene, the elastomer and the antioxidant into an internal mixer according to the proportion, banburying for 2-10 min at 140-200 ℃, then adding the vulcanizing agent, continuously banburying for 0.5-30 min, controlling the upper bolt pressure to be 10-100 MPa, and introducing the prepared material into a hopper for extrusion granulation to obtain the heat sealing material. In the internal mixer, the rotor speed is preferably 15 to 90rpm.
The preparation process takes poly fatty acid and elastomer as active components, unsaturated fatty acid controls the double bond position and quantity under the polymerization condition of the application, prepares renewable poly fatty acid with cross-linked fatty chain and carboxyl, introduces elastomer with specific structure, uses the molecular weight of active component fatty chain and copolypropylene to carry out entanglement, adds vulcanizing agent after banburying for a period of time, realizes dynamic vulcanization process, grafts more amorphous molecules with a certain structure onto polypropylene chain, damages the order of the polypropylene chain, promotes the formation of propylene chain segment gamma crystal, and solves the problems of low molecular weight component migration precipitation and roll sticking caused by traditional blending.
The object of a third aspect of the present application is to provide the use of the heat seal described above: the heat-sealing material is used as a heat-sealing layer material for biaxially oriented polypropylene films, heat-shrinkable polypropylene films and polypropylene casting films.
Compared with the prior art, the application has the following advantages:
(1) Low price, low initial heat sealing temperature below 75 ℃;
(2) The heat sealing temperature range is wide and can meet the requirements of different application scenes at 70-145 ℃;
(3) The hot tack strength is high: 13N/15mm, can meet the high-speed packaging requirement;
(4) The inclusion has excellent heat sealing property, and can meet the high-speed packaging process of powder and liquid;
(5) The material has high transparency and light transmittance of more than 90 percent;
(6) The obtained material has wide application in the fields of daily chemical products, foods, medicine packages and the like.
Detailed Description
The following detailed description of the preferred embodiments of the present application will provide a more clear understanding of the objects, features and advantages of the present application.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Parameters related to the embodiment of the scheme are tested by adopting the following standards and methods:
(1) The initial heat-sealing temperature, the hot tack strength and the heat-sealing temperature range of the material were determined using GB/T27740-2011. The sample strip is heated by a single knife, the heat sealing temperature is 116 ℃, the heat sealing pressure is 0.238MPa, the retention time is l s, the heat sealing times are 1 time, the test speed is set to 300mm/min, the gauge length is 50mm, the maximum load of the 5 samples when the samples are broken is recorded, and the average value of the maximum load of the 5 samples at 120 ℃ is the heat sealing strength of the material at 120 ℃; judging the initial heat sealing temperature, wherein if the heat sealing strength of the sample at a certain temperature is more than or equal to 3N/15mm and the heat sealing strength of the sample at a temperature lower than the certain temperature is less than 3N/15mm, the temperature is the initial heat sealing temperature of the sample; the heat-seal temperature range was determined by using a temperature range in which the heat-seal strength was higher than 9N/15 mm.
(2) The application adopts GB/T2410-2008 to test the light transmittance of the test sample.
(3) The inclusion heat sealability of the application is superior in that the heat sealing strength of the test material at 116 ℃ is reduced by 20 percent, the heat sealing strength is reduced by 20 to 40 percent, and the heat sealing strength is poor by more than 40 percent by dripping a certain paraffin oil at the center of the heat sealing film.
Example 1
(1) Polyoleic acid synthesis
100 parts by mass of oleic acid and 2 parts by mass of azobisisobutyronitrile were heated to 180℃and polymerized under stirring for 24 hours, and then distilled under reduced pressure (200℃1.33 KPa) for 4 hours to obtain a polymeric oleic acid.
(2) Preparation of heat-seal material
60 parts by weight of ethylene propylene butene terpolymer polypropylene (KS 407, BP, MI 5.0, MP 134 ℃ C.), 25 parts by weight of poly oleic acid, 5 parts by weight of linear low density polyethylene (2036G, tao Shidu Pont, MI 2.5, 0.935G/cm) 3 25 parts by weight of a polyethylene octene elastomer (7218 XEP, liande Basel, MI 6.0,0.9 g/cm) 3 ) And 2 parts by weight of an antioxidant 1010 at 160℃in a banburyingIn the machine, the speed of a rotor is controlled to be 20rpm for banburying for 5min, a uniformly mixed substance is obtained, 2 parts by weight of benzoyl peroxide is added, banburying is continued for 20min, and the upper plug pressure is controlled to be 18MPa. And (3) introducing the prepared material into a hopper, and extruding and granulating to obtain the heat-sealing material.
(3) Application of heat sealing material
The prepared heat-sealing material is prepared into a CPP heat-sealing film sample by a 3-layer coextrusion casting method, the thicknesses of the heat-sealing layer A, the core layer B and the corona layer C are respectively 5um, 15um and 5um, wherein the B layer and the C layer are homo-polypropylene (T36F), and the A layer is the prepared heat-sealing material.
The detection is carried out according to the detection standard, and the result is as follows:
the initial heat sealing temperature of the heat sealing material is 60 ℃, the heat sealing temperature of the material is 70-145 ℃, and the heat bonding strength is 15N/15mm; the light transmittance is 95%; inclusion heat sealability: and (3) the advantages are good.
Example 2
The procedure is as in example 1, with the difference that: different fatty acids were selected as shown in table 1.
Table 1: effect of different fatty acids on Heat seal Properties
The experimental results in table 1 above show that: when the preparation method is adopted to prepare the heat-sealing material, the biological oil selected in the table 1 can obtain better heat-sealing effect, the heat-sealing temperature can be basically controlled near 60 ℃, the temperature range is kept at 70-145 ℃, the span is kept at 70-75 ℃, and the heat-sealing strength is kept at 15-16N/15 min; the light transmittance is stably kept at 94-95%. Because the number of double bonds in eleostearic acid with the number of 2-7 is large, a highly crosslinked asphaltene component is easy to form in the polymerization process, the asphaltene component cannot be entangled with a polypropylene chain, no double bonds are arranged in stearic acid with the number of 2-6, an effective polymerization structure is difficult to form, and the product performance is poor.
Comparative example 1
The method of this comparative example is the same as example 1, except that: fatty acids were not polyaddited to illustrate the effect of the polyaromatic acids on heat seal performance, as follows:
60 parts by weight of ethylene propylene butene terpolymer polypropylene (KS 407, BP, MI 5.0, MP 134 ℃ C.) and 5 parts by weight of linear low density polyethylene (2036G, tao Shidu Pont, MI 2.5, 0.935G/cm) 3 25 parts by weight of a polyethylene octene elastomer (7218 XEP, liande Basel, MI 6.0,0.9 g/cm) 3 ) And 2 parts by weight of antioxidant 1010 are placed in an internal mixer at 160 ℃ and are banburying for 5min at a rotor speed of 20rpm to obtain a uniformly mixed substance, 2 parts by weight of benzoyl peroxide is added, banburying is continued for 20min, and the upper plug pressure is controlled to be 18MPa. And (3) introducing the prepared material into a hopper, and extruding and granulating to obtain the heat-sealing material.
Comparative example 1 was tested under the same conditions as example 1, and the results showed that: the heat sealing material obtained when no poly fatty acid is added has the initial heat sealing temperature of 115 ℃, the heat sealing temperature is far higher than the heat sealing temperature of the heat sealing material prepared by the application, the heat sealing temperature of the material is 125-140 ℃, the temperature is narrower, and the span is only 15 ℃; the heat-sealing strength of the glass is 7N/15mm, and the transmittance of the glass is 90% in the heat-sealing property of the inclusions, and is lower than that of the glass.
Comparative example 2
The method of this comparative example is the same as in example 1, except that: commercial dimer fatty acid (Shandong fine chemical Co., ltd., high grade pure GR) was used to illustrate the effect of the poly fatty acid preparation process on heat seal properties.
Compared to the heat seal prepared in example 1, the heat seal prepared in comparative example 2 using commercially available poly fatty acids has the following respective performance parameters: the initial heat-sealing temperature is 105 ℃, the heat-sealing temperature is far higher than the heat-sealing temperature of the heat-sealing material prepared by the application, the heat-sealing temperature range of the material is 120-135 ℃, the temperature range is narrower, and the span is only 15 ℃; the heat-sealing strength was 8N/15mm, and the light transmittance was 88% in the heat-sealing property of the inclusions.
Example 3
The procedure is as in example 1, with the difference that: different elastomers were chosen for the reaction as shown in table 2.
Table 2: impact of different elastomers on heat seal properties
As can be seen in connection with table 2: when the preparation method is adopted to prepare the heat seal material, the selected elastomer can obtain lower heat seal temperature (60-70 ℃) and wider temperature range (span about 65-75 ℃), the heat adhesion strength is basically kept between 15 and 16N/15min, and the light transmittance is also kept between 94 and 95 percent. Compared with the embodiment 1, the elastomer of the embodiment has a certain polar component, so that the thermal bonding efficiency of the material can be effectively improved. Too low (numbers 3-6, 3-7) would affect the mobility of the molecular weight and would not be well entangled with the copolypropylene chain.
Comparative example 3
The method of this comparative example is the same as example 1, except that: the elastomer is not added to illustrate the effect of the elastomer on the heat seal properties, and the specific process is as follows:
(1) Polyoleic acid synthesis
100 parts by mass of oleic acid and 2 parts by mass of azobisisobutyronitrile were heated to 180℃and polymerized under stirring for 24 hours, and then distilled under reduced pressure (200℃1.33 KPa) for 4 hours to obtain a polymeric oleic acid.
(2) Preparation of heat-seal material
60 parts by weight of ethylene propylene butene terpolymer polypropylene (KS 407, BP, MI 5.0, MP 134 ℃ C.), 25 parts by weight of poly oleic acid, 5 parts by weight of linear low density polyethylene (2036G, tao Shidu Pont, MI 2.5, 0.935G/cm) 3 Placing MP 125 ℃ and 2 parts by weight of antioxidant 1010 into an internal mixer at 160 ℃, controlling the speed of a rotor at 20rpm for banburying for 5min to obtain a uniformly mixed substance, adding 2 parts by weight of benzoyl peroxide, continuing banburying for 20min, and controlling the upper plug pressure to be 18MPa. Introducing the prepared material into a hopper, and extruding and granulatingAnd obtaining the heat sealing material.
This comparative example was tested under the same conditions as in example 1, and the results showed that: when no elastomer is added, the initial heat sealing temperature of the obtained heat sealing material is 115 ℃, which is far higher than the heat sealing temperature of the heat sealing material prepared by the application, the heat sealing temperature of the material is 120-135 ℃, the temperature is narrower, and the span is only 15 ℃; the hot tack strength is 8N/15mm and lower than that of the application; inclusion heat sealability, but light transmittance was 93%.
Example 4
The procedure is as in example 1, with the difference that: the different constituent copolymers were selected for the reaction, as specifically described in table 3.
Table 3: impact of different copolymer compositions on heat seal properties
Table 3 experiments were conducted with three copolymers as polypropylene, respectively, and compared with the terpolymer of example 1, the schemes corresponding to the sequence number 4-1 and the sequence number 4-2 can obtain lower heat sealing temperature and wider temperature range, and the heat sealing temperature is basically kept at 60-70 ℃; the temperature range span is about 65-75 ℃, the hot tack strength is basically kept at 15-16N/15 min, the light transmittance is kept at 94-95%, and compared with the terpolymer of the embodiment 1, the binary copolymer is easy to form a thick plate crystal structure due to better molecular regularity, so that the initial heat sealing temperature of the material is increased to some extent. The comonomer corresponding to the schemes of the serial numbers 4-4 and 4-5 has high melt index, low molecular weight, good fluidity, difficult formation of better entanglement with other components and easy crystallization to form more complete crystals, thus having high heat sealing temperature and poor light transmittance.
Example 5
The procedure is as in example 1, with the difference that: vulcanizing agents of different compositions were selected as shown in table 4.
Table 4: effect of different curatives on heat seal properties
Table 4, tested with different vulcanizing agents, compared with benzoyl peroxide of example 1, the corresponding schemes numbered 5-1 to 5-7 can achieve better vulcanizing effect, and then show that the finished heat seal has lower heat seal temperature (55-70 ℃), wider temperature range (65-75 ℃), higher hot tack strength (14-16N/15 min) and higher light transmittance (94-95%); the matched two-component curing agent has a better advantage in terms of initial heat seal temperature than the curing agent alone (see nos. 5-5, 5-6, 5-7 in table 4); in Table 4, the numbers 5-8 and 5-9 are too early in decomposition of the vulcanizing agent to uniformly vulcanize and early coke when applied to the present case scheme.
Example 6
The procedure is as in example 1, with the difference that: different structural antioxidants were selected as shown in table 5.
Table 5: impact of different antioxidants on heat seal properties
Table 5 is tested with several common antioxidants, and compared with antioxidant 1010 of example 1, the antioxidants corresponding to the above numbers 6-1 to 6-10 all have better antioxidant effect, and are shown that the finished heat seal material has lower heat seal temperature (60-75 ℃), wider temperature range (65-85 ℃), higher hot tack strength (14-17N/15 min) and higher light transmittance (94-95%); the matched two-component antioxidants have better synergistic advantages (see nos. 6-8, 6-9, 6-10 in table 5) compared to the antioxidants used alone and are shown to have better initial heat seal temperature, hot tack strength parameters; and when the serial numbers 6-11 and 6-12 in the table 5 are applied to the scheme of the present case, the problem of tolerance between the antioxidant and the system exists, so that oxidative crosslinking and coking are caused in the vulcanization process.
Comparative example 4: comparison with CN114292456A
The test was performed using the above standard with CN114292456a as comparative example 4 and analyzed with example 1 as shown in table 6.
Table 6: comparative example 4 and comparative example 1 Table
As shown in table 6, the difference between the two is mainly expressed by three aspects of composition, heat sealing effect and use effect:
first, differences in composition: in the example 1, the ternary polymerization polypropylene and the poly oleic acid are adopted as main reactions, and in the comparative example 4, the binary copolymer and the oleamide are adopted as main reactions; the present case contains an elastomer, a vulcanizing agent, and does not have the carbon fiber tube and magnesium oxide composite of comparative example 4.
Second, difference in heat sealing effect: including heat seal effects and application effects. As can be seen from Table 6, the heat sealing property, the hot tack strength, the light transmittance and the inclusion of the present case are far superior to those of the comparative examples.
Thirdly, the using effect is as follows: when the air column bag is used, the parameters of the air column bag are mainly the internal air pressure, about 0.07 megapascals, and the pressure can be 769.7-803.3N; the internal pressure of the present case was about 0.07 mpa, and the pressure-bearing pressure was 1051 to 1136N (the parameter when the air column bag was used according to the application of example 1), which was superior to that of comparative example 4.
The reason for the difference is mainly that: the heat sealing material provided by the scheme takes the composite of the poly oleic acid and the polyolefin resin as main components, the ultra-low initial heat sealing temperature and the wide heat sealing temperature range are endowed to the material, the main reaction generated by the heat sealing material is different from that of comparative example 4 mainly in that the poly oleic acid is used for forming a cross-linked fatty chain and carboxyl structure, the heat sealing material can be effectively entangled with polypropylene, and the polar polycarboxylic acid structure can effectively increase the heat adhesion performance of the material; compared with the carbon fiber tube and magnesium oxide compound in the comparative example 4, the scheme also introduces a vulcanizing agent and an antioxidant, forms gamma crystals in a propylene chain segment, greatly reduces migration and precipitation of low molecular weight components, and is characterized in that the product has smooth surface and higher strength when applied to a gas column bag.
Comparative example 5: comparison with CN101758652A
The test was performed using the above standard with CN101758652a as comparative example 4, and the analysis was performed with example 1, as shown in table 7.
Table 7: comparative example 5 and comparative example 1 Table
As shown in table 7, the difference between the two is mainly expressed by three aspects of composition, heat sealing effect and usage pattern:
first, differences in composition: in the example 1, the ternary polymerization polypropylene and the poly oleic acid are adopted as main reactions, and in the comparative example 5, the metallocene polyethylene and the erucamide are adopted as main reactions; the scheme comprises a polyethylene octene elastomer, an antioxidant and a benzoyl peroxide vulcanizing agent, but does not comprise a slipping agent, ammonium ethoxide and other surfactants of comparative example 5, and linear low-density polyethylene is used, which is different from metallocene polyethylene.
Second, heat sealing effect: as can be seen from the performance parameters of the heat-seal layer of comparative example 5 (corresponding to the functional layer in the three-layer structure of comparative example 5) in table 5, the heat-seal performance in the present case is not greatly different in heat-seal temperature, but Wen Yuyuan of comparative example 5 is smaller than that in the present case; the hot tack strength, light transmittance and inclusion were also far superior to comparative example 5.
Thirdly, the use mode is as follows: when in use, the material is mainly aimed at the PP film with high strength. Comparative example 5 was mainly applied to PE films, with a large difference from the application field of this case.
The reason for the difference is mainly that: compared with metallocene polyethylene and erucamide of comparative example 5, the scheme takes the poly fatty acid and polyolefin resin compound as main components, the endowed material has ultralow initial heat sealing temperature and wide heat sealing temperature range, the main reaction of the two schemes is mainly characterized in that the poly fatty acid is used for forming a structure with crosslinked fatty chains and carboxyl groups, the poly fatty acid can be effectively entangled with polypropylene, and the polar polycarboxylic acid structure can effectively increase the heat viscosity of the material; the winding fastness of the fatty chain is enhanced by matching the elastomer with the polyolefin resin, namely the copolymerized polypropylene, and compared with the fact that the slipping agent and the ammonium ethoxide adopted in the comparative example 5 exist small molecules outside, the vulcanizing agent and the antioxidant matched with the scheme form gamma crystals in a propylene chain segment, migration and precipitation of low-molecular-weight components are greatly reduced, and the product is smooth in surface and high in strength when the product is applied to a stretched film.

Claims (2)

1. The ultralow-temperature heat sealing material for polypropylene is characterized by being prepared by vulcanizing, extruding and granulating the following components in proportion:
40 to 80 parts by weight of copolymerized polypropylene,
4 to 40 parts by weight of poly fatty acid,
5 to 20 parts by weight of low-density polyethylene,
5 to 45 parts by weight of an elastomer,
1 to 2 parts by weight of a vulcanizing agent,
0.5 to 4 parts by weight of an antioxidant,
the polypropylene copolymer is one or more than one of ethylene propylene binary copolymer, butene propylene binary copolymer and ethylene propylene butene ternary copolymer,
the elastomer is one or more than one of ethylene propylene diene monomer, ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-sodium acrylate copolymer, styrene-butadiene block copolymer and pentylene block copolymer,
the vulcanizing agent is one or more of benzoyl peroxide, dicumyl peroxide, benzoic peroxide, methyl ethyl ketone peroxide, neodecanoic peroxide and tert-butyl peroxypivalate,
the antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, butyl hydroxyanisole, dibutyl hydroxytoluene, propyl gallate and tert-butyl hydroquinone,
the ultralow temperature heat sealing material for polypropylene is prepared by the following steps:
(1) Preparation of poly fatty acid: charging unsaturated fatty acid and azodiisobutyronitrile according to the mass ratio of 100:1-3, heating to 130-230 ℃, stirring and polymerizing for 10-24 h, then decompressing and distilling for 1-6 h to obtain poly fatty acid,
the unsaturated fatty acid is one or more of oleic acid, decenoic acid, myrcenoic acid, myristoleic acid, erucic acid, linoleic acid, decadienoic acid and linolenic acid;
(2) Preparing a heat sealing material: adding the poly fatty acid, the copolymerized polypropylene, the low-density polyethylene, the elastomer and the antioxidant into an internal mixer according to a proportion, banburying for 2-10 min at 140-200 ℃, then adding the vulcanizing agent, continuously banburying for 0.5-30 min, controlling the pressure of an upper bolt to be 10-100 MPa, introducing the prepared material into a hopper, and extruding and granulating to obtain the heat sealing material;
the initial heat sealing temperature of the ultralow temperature heat sealing material for polypropylene is below 75 ℃; the heat sealing temperature of the material is 70-145 ℃, and the material is used as a heat sealing layer material for biaxially oriented polypropylene film, heat shrinkage polypropylene film or polypropylene casting film, and the heat bonding strength of the material is more than 13N/15mm.
2. An ultra-low temperature heat seal for polypropylene according to claim 1, wherein: the density of the low-density polyethylene is 0.910-0.925 g/cm 3 The general low density polyethylene has a density of 0.918-0.940 g/cm 3 Either or a mixture of both of the linear low density polyethylenes.
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