阅读说明：本技术 一种多层共挤薄膜用粘合树脂及其制备方法 (Adhesive resin for multilayer co-extruded film and preparation method thereof ) 是由 李昌华 孙永健 张海平 于 2020-12-31 设计创作，主要内容包括：本发明提供了一种多层共挤薄膜用粘合树脂及其制备方法,属于粘合树脂技术领域。所述粘合树脂原料为聚烯烃树脂、光引发剂、接枝物、多官能团助接枝剂、其他加工助剂。其具体制备方法为：将聚烯烃树脂、光引发剂、接枝物、多官能团助接枝剂及其他加工助剂,加入混合机中混合均匀；将上述混合物料投入双螺杆挤出机中混炼、挤出拉条,处于热熔体的料条通过紫外光辐照灯,进行辐照接枝,料条再经过冷却、切粒得到多层共挤薄膜用粘合树脂。本发明共挤薄膜用粘合树脂的制备方法是在螺杆外进行接枝,解决了产品易产生凝胶和焦料的问题。而且可以通过调整配方、紫外灯辐照强度和紫外灯管长度来控制接枝率,生产高接枝率产品。(The invention provides adhesive resin for a multilayer co-extruded film and a preparation method thereof, belonging to the technical field of adhesive resin. The raw materials of the adhesive resin are polyolefin resin, a photoinitiator, a graft, a polyfunctional group grafting aid and other processing aids. The specific preparation method comprises the following steps: adding polyolefin resin, a photoinitiator, a graft, a polyfunctional group grafting aid and other processing aids into a mixer and uniformly mixing; and (3) putting the mixed material into a double-screw extruder for mixing and extruding bracing strips, irradiating and grafting the material strips in the hot melt through an ultraviolet light irradiation lamp, and cooling and dicing the material strips to obtain the adhesive resin for the multilayer co-extruded film. The preparation method of the adhesive resin for the co-extruded film, disclosed by the invention, is to graft outside the screw, so that the problem that the product is easy to generate gel and coke materials is solved. And the grafting rate can be controlled by adjusting the formula, the irradiation intensity of an ultraviolet lamp and the length of an ultraviolet lamp tube, so that a product with high grafting rate is produced.)

1. The adhesive resin for the multilayer coextruded film is characterized by comprising the following raw materials in percentage by mass:

2. the adhesive resin for a multilayer coextruded film according to claim 1, wherein the polyolefin resin comprises a saturated polyolefin resin and/or an unsaturated polyolefin resin.

3. The adhesive resin for a multilayer coextruded film as claimed in claim 1, wherein the photoinitiator is a radical photoinitiator; preferably at least one of BP, 184, MK, CTX or IPBE.

4. The adhesive resin for a multilayer coextruded film according to claim 1, wherein the graft is at least one of maleic anhydride, glycidyl acrylate, maleic acid or acrylic acid.

5. The adhesive resin for multilayer coextruded films as claimed in claim 1, wherein the polyfunctional co-grafting agent is a reactive monomer having two or more reactive olefinic functional groups; preferably at least one of TMPTA, TAIC, TMPTMA, PETA, DPHA or DPPA.

6. The adhesive resin for a multilayer coextruded film as claimed in claim 1, wherein the other processing aid is one or more of an antioxidant, a dispersant or a lubricant.

7. The adhesive resin for a multilayer co-extruded film according to claim 6, wherein the antioxidant is at least one of 1010, DLTP, 168, 1035, or 300; the dispersing agent is at least one of polyethylene wax, stearic acid or polypropylene wax; the lubricant is at least one of silicone oil, white oil or PPA.

8. A method for preparing the adhesive resin for the multilayer co-extruded film as defined in any one of claims 1 to 7, wherein the method comprises the steps of:

(1) adding polyolefin resin, a photoinitiator, a graft, a polyfunctional group grafting aid and other processing aids into a mixer and uniformly mixing;

(2) and (3) putting the mixed material into a double-screw extruder for mixing and extruding bracing strips, irradiating and grafting the material strips in the hot melt through an ultraviolet light irradiation lamp, and cooling and dicing the material strips to obtain the adhesive resin for the multilayer co-extruded film.

9. The process of claim 1, wherein in step (2) the UV radiation lamp has a wavelength of 365nm and a lamp energy level of 10J/cm²The light irradiation time was 15 s.

Technical Field

The invention belongs to the technical field of adhesive resin, and particularly relates to adhesive resin for a multilayer co-extruded film and a preparation method thereof.

Background

With the continuous improvement of the comprehensive properties of the film and the mature development of the co-extrusion technology, the multilayer structure film is a common design. The use of different materials in each layer allows for the integration of properties to provide multiple properties simultaneously on a single film. However, materials of different characteristics often do not have good affinity. Therefore, a material is needed to combine them to ensure the peeling force between the layers, and the material is the adhesive resin.

There are generally two methods of producing the adhesive resin for multilayer coextruded films. The first one is copolymerization, which is prepared by polymerizing monomers in a reaction kettle, and has large equipment investment and difficult process technology. The products are mainly imported, such as EAA and the like, and are expensive. The second one is blending melt grafting, only a double-screw extruder is needed, the equipment investment is low, and the process is simple. However, this method also has many disadvantages. The fluidity of the resin is poor after grafting, dead glue is easily formed in a screw after continuous production for a long time and is randomly brought out along with a melt, so that gel and coke materials exist in the adhesive resin, and fish eyes or crystal points are easily formed on a film produced by using the adhesive resin. And after the machine is stopped due to faults, the materials are still in the screw, so that the machine must be stopped to clean the screw due to resin crosslinking, and the production efficiency is greatly influenced. The blending melt grafting is limited by the length of a screw and the extrusion temperature, and the grafting rate of the product is generally about 1 percent at most.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides an adhesive resin for a multilayer co-extruded film and a preparation method thereof. The preparation method of the adhesive resin for the co-extruded film, disclosed by the invention, is to graft outside the screw, so that the problem that the product is easy to generate gel and coke materials is solved. And the grafting rate can be controlled by adjusting the formula, the irradiation intensity of an ultraviolet lamp and the length of an ultraviolet lamp tube, so that a product with high grafting rate is produced.

The technical scheme of the invention is as follows:

the adhesive resin for the multilayer coextruded film comprises the following raw materials in percentage by mass:

the polyolefin resin includes a saturated polyolefin resin and/or an unsaturated polyolefin resin.

The photoinitiator is a free radical photoinitiator; preferably at least one of BP, 184, MK, CTX or IPBE.

The graft is at least one of maleic anhydride, glycidyl acrylate, maleic acid or acrylic acid.

The polyfunctional group grafting aid is an active monomer with two or more active alkene functional groups; preferably at least one of TMPTA, TAIC, TMPTMA, PETA, DPHA or DPPA.

The other processing aids are one or more of antioxidants, dispersants or lubricants.

The antioxidant is at least one of 1010, DLTP, 168, 1035 or 300; the dispersant is at least one of polyethylene wax, stearic acid or polypropylene wax; the lubricant is at least one of silicone oil, white oil or PPA.

A preparation method of adhesive resin for a multilayer co-extruded film comprises the following steps:

(1) adding polyolefin resin, a photoinitiator, a graft, a polyfunctional group grafting aid and other processing aids into a mixer and uniformly mixing;

(2) and (3) putting the mixed material into a double-screw extruder for mixing and extruding bracing strips, irradiating and grafting the material strips in the hot melt through an ultraviolet light irradiation lamp, and cooling and dicing the material strips to obtain the adhesive resin for the multilayer co-extruded film.

The wavelength of the ultraviolet radiation lamp in the step (2) is 365nm, and the energy position of the lamp is 10J/cm²The illumination time was 15 s.

The beneficial technical effects of the invention are as follows:

the material in the invention has only mixing effect in the double-screw extruder, and the flowability of the material in the screw is basically unchanged. After the materials are extruded, the melt is irradiated by an ultraviolet lamp, the photoinitiator is excited and cracked to generate free radicals, graft is initiated to be grafted to a polyolefin molecular chain, and the graft is grafted outside a screw, so that the problem that the product is easy to generate gel and coke materials is solved. Because the grafting is carried out outside the screw, the grafting is not influenced by the factors such as melt flow rate, incomplete grafting reaction in the screw and the like, and the high-grafting-rate product can be produced by increasing the using amounts of the photoinitiator, the grafting assistant and the like and improving the irradiation energy and time.

Detailed Description

The present invention will be described in detail with reference to examples.

Examples 1 to 3: the preparation method of the adhesive resin for the multilayer coextruded film is characterized in that the adhesive resin for the multilayer coextruded film is used for the multilayer coextruded film and comprises the following components in parts by weight:

TABLE 1

	Example 1	Example 2	Example 3
				Polyolefin resin	100 portions of	100 portions of	100 portions of
Photoinitiator	0.01 part	0.03 part	0.1 part
				Graft material	0.5 portion	1 part of	3 portions of
Polyfunctional group grafting aid	0.01 part	0.03 part	0.1 part
				Other auxiliaries	1 part of	1.5 parts of	2 portions of

In example 1, the polyolefin resin was a polyethylene butadiene resin, the photoinitiator was 184, the graft was maleic anhydride, the polyfunctional group co-grafting agent was TAIC, the antioxidant was 1010, the dispersant was polyethylene wax, and the lubricant was silicone oil. In example 2, the polyolefin resin is ethylene-butylene copolymer resin, the photoinitiator is 369, the graft is maleic acid, the polyfunctional group co-grafting agent is TMPTMA, the antioxidant is DLTP, the dispersant is stearic acid, and the lubricant is white oil. In example 3, the polyolefin resin is polyethylene resin, the photoinitiator is BP, the graft is glycidyl acrylate, the polyfunctional group co-grafting agent is TMPTA, the antioxidant is 1035, the dispersant is polypropylene wax, and the lubricant is PPA.

The adhesive resin for the multilayer co-extruded film is prepared by the following steps:

(1) weighing the polyolefin resin, the photoinitiator, the graft, the multifunctional group grafting aid and other processing aids in the formula according to the weight ratio, and adding the materials into a high-speed mixer for uniformly mixing;

(2) mixing the above mixed materials in a twin-screw extruder, extruding into strips, irradiating and grafting the strips in hot melt by an ultraviolet radiation lamp, cooling and cutting into granules to obtain the materials of example 1, example 2 and example 3, wherein the wavelength of the ultraviolet radiation lamp is 365nm, and the energy position of the lamp is 10J/cm²The illumination time was 15 s.

Comparative examples 1 to 2: the preparation method of the adhesive resin for the multilayer coextruded film is characterized in that the adhesive resin for the multilayer coextruded film is used for the multilayer coextruded film and comprises the following components in parts by weight:

TABLE 2

	Comparative example 1	Comparative example 2
			Polyolefin resin	100 portions of	100 portions of
Photoinitiator	0 portion of	0 portion of
			Thermal decomposition of peroxides	0.03 part	0.1 part
Graft material	1 part of	3 portions of
			Polyfunctional group grafting aid	0.03 part	0.1 part
Other auxiliaries	1.5 parts of	2 portions of

The adhesive resin for the multilayer coextruded film is prepared by the following steps of comparative example 1 and comparative example 2:

(1) weighing the polyolefin resin, the thermal decomposition peroxide, the graft, the polyfunctional group grafting aid and other processing aids in the formula according to the weight ratio, and adding the materials into a high-speed mixer for uniformly mixing;

(2) and (3) putting the mixed material into a double-screw extruder, mixing, grafting, drawing strips, cooling and cutting into granules to obtain a comparative example 1 and a comparative example 2.

Comparative examples 1 to 2:

comparative example 1, prepared according to the protocol of example 2, except that the photoinitiator was changed to equal amount of thermally decomposed peroxide, and the ultraviolet grafting process was removed during the preparation process, and melt grafting was performed in a screw to obtain comparative example 1;

comparative example 2 was prepared according to the procedure of example 3, except that the photoinitiator was changed to an equivalent amount of thermally decomposed peroxide, and the ultraviolet light grafting process was removed during the preparation process, and melt grafting in a screw was used to obtain comparative example 2.

The grafting rate is determined according to the standard Q/HCHX 3-2016; according to a visual method, after continuous production is carried out for 7 days, 100 particles are taken, and the number of coke particles in the particles is detected; the melt index was measured at 190 ℃ under 2.16kg conditions in accordance with GB/T3682-2018. The performance test data of the adhesive resin for the multilayer co-extruded film prepared in each of examples 1 to 3 and comparative examples 1 to 2 are as follows:

TABLE 3

As shown in Table 3, in the examples of the present invention, compared with comparative examples 1 and 2, after 7 days of continuous production, no coke was present in the particles, indicating that the ultraviolet irradiation grafting technique can substantially prevent the generation of coke during the continuous production; example 2 compared with comparative example 1 and comparative example 2, respectively, the grafting rate was greatly improved under the condition of the same amount of added grafts, which indicates that the grafting rate is greatly improved by ultraviolet irradiation grafting; example 2 compared with comparative example 2, the melt flow rate change rate is smaller, and the side surface reflects that ultraviolet light irradiation grafting can reduce cross-linked gel.

Therefore, the preparation method of the adhesive resin for the multilayer co-extrusion film, disclosed by the invention, has the advantages that the traditional melt grafting is replaced by the ultraviolet grafting technology, and the grafting is carried out outside the screw, so that the problem that the product is easy to generate gel and coke materials is solved. And the grafting rate can be controlled by adjusting the formula, the irradiation intensity of an ultraviolet lamp and the length of an ultraviolet lamp tube, so that a product with high grafting rate is produced.

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.