阅读说明：本技术 一种耐低温可拉伸的柔性热熔胶及其制备方法 (Low-temperature-resistant stretchable flexible hot melt adhesive and preparation method thereof ) 是由 刘雄英 于 2021-10-28 设计创作，主要内容包括：本发明公开了一种耐低温可拉伸的柔性热熔胶及其制备方法,涉及热熔胶技术领域,其技术方案要点是：由以下重量份的组分组成：基础树脂100份、增粘剂60-80份、调节剂10-20份、塑料助剂2-4份以及填料20-30份；所述基础树脂为丁基橡胶；所述增粘剂为有机硅改性环氧树脂、聚甲基丙烯酸甲酯、间规聚苯乙烯与聚乙烯嵌段共聚物的混合物；所述塑料助剂为紫外光吸收剂。本发明实现了有机硅改性环氧树脂二次改性,有效增强了耐低温热熔胶在低温环境下的柔性和可拉伸性能,具有更广的应用前景；在-50℃情况下仍具有高达260％的拉伸性能。(The invention discloses a low-temperature-resistant stretchable flexible hot melt adhesive and a preparation method thereof, relating to the technical field of hot melt adhesives, and the key points of the technical scheme are as follows: the composition comprises the following components in parts by weight: 100 parts of base resin, 60-80 parts of tackifier, 10-20 parts of regulator, 2-4 parts of plastic additive and 20-30 parts of filler; the base resin is butyl rubber; the tackifier is a mixture of organic silicon modified epoxy resin, polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer; the plastic additive is an ultraviolet absorber. The invention realizes the secondary modification of the organic silicon modified epoxy resin, effectively enhances the flexibility and the stretchability of the low-temperature resistant hot melt adhesive in a low-temperature environment, and has wider application prospect; still have tensile properties of up to 260% at-50 ℃.)

1. The low-temperature-resistant stretchable flexible hot melt adhesive is characterized by comprising the following components in parts by weight: 100 parts of base resin, 60-80 parts of tackifier, 10-20 parts of regulator, 2-4 parts of plastic additive and 20-30 parts of filler;

the base resin is butyl rubber;

the tackifier is a mixture of organic silicon modified epoxy resin, polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer;

the plastic additive is an ultraviolet absorber.

2. The low-temperature-resistant stretchable flexible hot melt adhesive according to claim 1, wherein the organosilicon modified epoxy resin is prepared from bisphenol propylene epoxy resin and dimethyl polysiloxane through a condensation reaction.

3. The low-temperature-resistant stretchable flexible hot melt adhesive according to claim 1, wherein the molar ratio of the organic silicon modified epoxy resin, the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer in the tackifier is 6:3: 1.

4. The low temperature resistant stretchable flexible hot melt adhesive according to claim 1, wherein the regulator is paraffin.

5. The low temperature resistant stretchable flexible hot melt adhesive according to claim 1, wherein the filler is talc.

6. A preparation method of a low-temperature-resistant stretchable flexible hot melt adhesive is characterized in that the preparation method is applied to the low-temperature-resistant stretchable flexible hot melt adhesive in any one of claims 1 to 5, and comprises the following steps:

s1: weighing the raw materials according to the configured weight parts, heating, melting, stirring and mixing the base resin and the organic silicon modified epoxy resin, adding part of the filler, and continuously stirring and mixing to obtain a first-grade mixture;

s2: adding polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer and ultraviolet absorbent into the first-stage mixture in sequence, heating, stirring and mixing, wherein the ultraviolet absorbent promotes the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer to be grafted and crosslinked with organic silicon modified epoxy resin and butyl rubber, and cooling to obtain a second-stage mixture;

s3: adding the regulator and the rest part of the filler into the secondary mixture, stirring and mixing, cooling, and extruding to obtain the low-temperature-resistant stretchable flexible hot melt adhesive.

7. The method for preparing the low-temperature-resistant stretchable flexible hot melt adhesive according to claim 6, wherein the filler is added in the ratio of S1 to S3 of 7: 3.

8. The preparation method of the low-temperature-resistant stretchable flexible hot melt adhesive according to claim 6, wherein the ultraviolet absorber is an organic ultraviolet absorber.

9. The method for preparing the low temperature resistant stretchable flexible hot melt adhesive according to claim 6, wherein in step S1, the heating temperature is 110-120 ℃, and the stirring and mixing time is 60-100 min.

10. The method as claimed in claim 6, wherein in step S2, the temperature is raised to 130-150 ℃, the mixing time is 60-80min, and the temperature is lowered to 100-120 ℃.

Technical Field

The invention relates to the technical field of hot melt adhesives, in particular to a low-temperature-resistant stretchable flexible hot melt adhesive and a preparation method thereof.

Background

Hot melt adhesive is a plastic adhesive, is in a solid state at normal temperature, can be quickly bonded after being heated and melted, has been rapidly developed in many fields, particularly has been used for replacing nail-mounting and wire-mounting in printing, packaging and other industries, and is beginning to be used in the fields of buildings, airplanes, ships, automobile interior decoration and the like. The performance of the hot melt adhesive is changed along with the change of the temperature, and when the temperature is increased to a certain high temperature or decreased to a certain low temperature, the performance of the hot melt adhesive is reduced, so that the bonding strength of the material is weakened, and the strength of the material is finally influenced, so that high requirements on high temperature resistance and low temperature resistance of the hot melt adhesive are met, for example, an automobile running at the temperature of-30 ℃ is easy to break if the low temperature resistance of the hot melt adhesive attached to the automobile is poor. For example, when a hot melt adhesive tape is used for pipe bonding in a low temperature environment (-30 ℃), the tape tends to break when the hot melt adhesive tape is spread when its low temperature resistance is poor.

At present, the common low-temperature-resistant hot melt adhesives mainly comprise polyamide hot melt adhesives and hot melt adhesives prepared by taking butyl rubber as basic rubber. The main components of the hot melt adhesive prepared by taking butyl rubber as basic rubber generally comprise tackifying resin, filler, regulator and antioxidant, wherein the tackifying resin is petroleum resin, rosin resin and the like; and also in part by mixing butyl rubber with epoxy resin. Although the low-temperature-resistant hot melt adhesive in the prior art has certain low-temperature resistance and flexibility, the applied environment is more and more complex along with the continuous development of the hot melt adhesive, so that higher requirements are put forward on the low-temperature-resistant hot melt adhesive.

Therefore, the research and design of the low-temperature-resistant stretchable flexible hot melt adhesive and the preparation method thereof are the problems which are urgently needed to be solved at present.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide a low-temperature-resistant stretchable flexible hot melt adhesive and a preparation method thereof.

The technical purpose of the invention is realized by the following technical scheme:

in a first aspect, the low-temperature-resistant stretchable flexible hot melt adhesive is composed of the following components in parts by weight: 100 parts of base resin, 60-80 parts of tackifier, 10-20 parts of regulator, 2-4 parts of plastic additive and 20-30 parts of filler;

the base resin is butyl rubber;

the tackifier is a mixture of organic silicon modified epoxy resin, polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer;

the plastic additive is an ultraviolet absorber.

Preferably, the organosilicon modified epoxy resin is prepared from bisphenol propane epoxy resin and dimethyl polysiloxane through a condensation reaction.

Preferably, the mol ratio of the organic silicon modified epoxy resin, the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer in the tackifier is 6:3: 1.

Preferably, the modifier is paraffin.

Preferably, the filler is talc.

In a second aspect, a preparation method of a low-temperature-resistant stretchable flexible hot melt adhesive is provided, and the preparation method is applied to any one of the low-temperature-resistant stretchable flexible hot melt adhesives in the first aspect, and comprises the following steps:

s1: weighing the raw materials according to the configured weight parts, heating, melting, stirring and mixing the base resin and the organic silicon modified epoxy resin, adding part of the filler, and continuously stirring and mixing to obtain a first-grade mixture;

s2: adding polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer and ultraviolet absorbent into the first-stage mixture in sequence, heating, stirring and mixing, wherein the ultraviolet absorbent promotes the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer to be grafted and crosslinked with organic silicon modified epoxy resin and butyl rubber, and cooling to obtain a second-stage mixture;

s3: adding the regulator and the rest part of the filler into the secondary mixture, stirring and mixing, cooling, and extruding to obtain the low-temperature-resistant stretchable flexible hot melt adhesive.

Preferably, the filler is added in a ratio of 7:3 in S1, S3.

Preferably, the ultraviolet light absorber is an organic ultraviolet light absorber.

Preferably, in step S1, the heating temperature is 110 ℃ to 120 ℃, and the stirring and mixing time is 60 min to 100 min.

Preferably, in step S2, the temperature raising is 130-150 ℃, the stirring and mixing time is 60-80min, and the temperature lowering is 100-120 ℃.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the low-temperature-resistant stretchable flexible hot melt adhesive provided by the invention, the chemical component design is carried out on the components, the mixture of the organic silicon modified epoxy resin, the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer is used as a tackifier, the organic silicon modified epoxy resin is firstly melted and mixed with the butyl rubber, and then the corresponding polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer and the ultraviolet absorber are added, so that the organic silicon modified epoxy resin and a base tree can be grafted and crosslinked, the secondary modification of the organic silicon modified epoxy resin is realized, the flexibility and the stretchability of the low-temperature-resistant hot melt adhesive in a low-temperature environment are effectively enhanced, and the low-temperature-resistant stretchable flexible hot melt adhesive has a wider application prospect;

2. according to the preparation method of the low-temperature-resistant stretchable flexible hot melt adhesive, provided by the invention, the butyl rubber, the organic silicon modified epoxy resin, the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer are subjected to distribution and fusion, and the filler with a corresponding proportion is added in the two fusion processes, so that the uniformity of the prepared low-temperature-resistant hot melt adhesive can be effectively improved, and the low-temperature-resistant stretchable flexible hot melt adhesive still has the stretching performance of up to 260% at the temperature of-50 ℃.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to examples and comparative examples, and the exemplary embodiments and descriptions thereof are only for explaining the present invention and are not intended to limit the present invention.

Example 1

The low-temperature-resistant stretchable flexible hot melt adhesive is prepared from the following components in parts by weight: 100 parts of butyl rubber, 36 parts of organic silicon modified epoxy resin, 18 parts of polymethyl methacrylate, 6 parts of syndiotactic polystyrene and polyethylene block copolymer, 10 parts of paraffin, 2 parts of organic ultraviolet absorber and 20 parts of talcum powder.

In this embodiment, the silicone-modified epoxy resin is prepared from bisphenol-based propylene oxide resin and dimethylpolysiloxane by a condensation reaction.

The preparation method of the flexible hot melt adhesive comprises the following steps:

s1: weighing the raw materials according to the configured weight parts, heating the base resin and the organic silicon modified epoxy resin to 110-120 ℃, melting, stirring and mixing for 60-100min, adding 70% of filler, and continuously stirring and mixing to obtain a first-grade mixture;

s2: sequentially adding polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer and ultraviolet absorber into the primary mixture, heating to 130-150 ℃, stirring and mixing for 60-80min, wherein the ultraviolet absorber promotes the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer to be grafted and crosslinked with organic silicon modified epoxy resin and butyl rubber, and cooling to 100-120 ℃ to obtain a secondary mixture;

s3: adding the regulator and the rest 30% of filler into the secondary mixture, stirring and mixing, cooling, and extruding to obtain the low-temperature-resistant stretchable flexible hot melt adhesive.

Example 2

The low-temperature-resistant stretchable flexible hot melt adhesive is prepared from the following components in parts by weight: 100 parts of butyl rubber, 48 parts of organic silicon modified epoxy resin, 24 parts of polymethyl methacrylate, 8 parts of syndiotactic polystyrene and polyethylene block copolymer, 20 parts of paraffin, 4 parts of organic ultraviolet absorber and 30 parts of talcum powder;

in this embodiment, the silicone-modified epoxy resin is prepared from bisphenol-based propylene oxide resin and dimethylpolysiloxane by a condensation reaction.

The preparation method of the flexible hot melt adhesive comprises the following steps:

s1: weighing the raw materials according to the configured weight parts, heating the base resin and the organic silicon modified epoxy resin to 110-120 ℃, melting, stirring and mixing for 60-100min, adding 70% of filler, and continuously stirring and mixing to obtain a first-grade mixture;

s2: sequentially adding polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer and ultraviolet absorber into the primary mixture, heating to 130-150 ℃, stirring and mixing for 60-80min, wherein the ultraviolet absorber promotes the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer to be grafted and crosslinked with organic silicon modified epoxy resin and butyl rubber, and cooling to 100-120 ℃ to obtain a secondary mixture;

s3: adding the regulator and the rest 30% of filler into the secondary mixture, stirring and mixing, cooling, and extruding to obtain the low-temperature-resistant stretchable flexible hot melt adhesive.

Example 3

The low-temperature-resistant stretchable flexible hot melt adhesive is prepared from the following components in parts by weight: 100 parts of butyl rubber, 42 parts of organic silicon modified epoxy resin, 21 parts of polymethyl methacrylate, 7 parts of syndiotactic polystyrene and polyethylene block copolymer, 15 parts of paraffin, 3 parts of organic ultraviolet absorber and 25 parts of talcum powder;

in this embodiment, the silicone-modified epoxy resin is prepared from bisphenol-based propylene oxide resin and dimethylpolysiloxane by a condensation reaction.

The preparation method of the flexible hot melt adhesive comprises the following steps:

s1: weighing the raw materials according to the configured weight parts, heating the base resin and the organic silicon modified epoxy resin to 110-120 ℃, melting, stirring and mixing for 60-100min, adding 70% of filler, and continuously stirring and mixing to obtain a first-grade mixture;

s2: sequentially adding polymethyl methacrylate, syndiotactic polystyrene and polyethylene block copolymer and ultraviolet absorber into the primary mixture, heating to 130-150 ℃, stirring and mixing for 60-80min, wherein the ultraviolet absorber promotes the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer to be grafted and crosslinked with organic silicon modified epoxy resin and butyl rubber, and cooling to 100-120 ℃ to obtain a secondary mixture;

s3: adding the regulator and the rest 30% of filler into the secondary mixture, stirring and mixing, cooling, and extruding to obtain the low-temperature-resistant stretchable flexible hot melt adhesive.

Comparative example 1

100 parts of butyl rubber, 70 parts of organic silicon modified epoxy resin, 15 parts of paraffin, 3 parts of 264 antioxidant and 25 parts of talcum powder.

The preparation method comprises the following steps: weighing the raw materials according to the configured weight parts, heating all the raw materials to 110-150 ℃ for melting, stirring and mixing for 2-3h, cooling, and extruding to obtain the corresponding hot melt adhesive.

Comparative example 2

100 parts of butyl rubber, 70 parts of organic silicon modified epoxy resin, 15 parts of paraffin, 3 parts of organic ultraviolet absorber and 25 parts of talcum powder.

The preparation method comprises the following steps: weighing the raw materials according to the configured weight parts, heating all the raw materials to 110-150 ℃ for melting, stirring and mixing for 2-3h, cooling, and extruding to obtain the corresponding hot melt adhesive.

Comparative example 3

100 parts of butyl rubber, 42 parts of organic silicon modified epoxy resin, 21 parts of polymethyl methacrylate, 7 parts of syndiotactic polystyrene and polyethylene block copolymer, 15 parts of paraffin, 3 parts of 264 antioxidant and 25 parts of talcum powder.

The preparation method comprises the following steps: weighing the raw materials according to the configured weight parts, heating all the raw materials to 110-150 ℃ for melting, stirring and mixing for 2-3h, cooling, and extruding to obtain the corresponding hot melt adhesive.

Experimental testing

The hot melt adhesives prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for adhesion (GB/T2971), low temperature flexibility and elongation at break, respectively, in accordance with the industry standard, such as ASTM D638. The test results are shown in table 1. The low-temperature flexibility test is an ultimate temperature value at which a fracture occurs in a non-stretched state. The elongation at break is the tensile elongation at a temperature of-50 ℃.

TABLE 1

It can be seen from comparative examples 1 and 2 that there is no significant difference in adhesion, low temperature flexibility, and elongation at break between the organic ultraviolet absorber and the 264 antioxidant with respect to the hot melt adhesive obtained by fusing the butyl rubber and the silicone-modified epoxy resin.

It can be seen from comparative example 3, comparative example 1 and comparative example 2 that the fusion of the butyl rubber, the silicone-modified epoxy resin, the polymethyl methacrylate, the syndiotactic polystyrene and the polyethylene block copolymer improves the low-temperature flexibility and the elongation at break to a certain extent, but the adhesive strength is not significantly different at the same component content.

As can be seen from examples 1-3 and comparative examples 1-3, under the action of the organic ultraviolet absorber, the graft crosslinking between the butyl rubber and the organosilicon modified epoxy resin and the block copolymer of polymethyl methacrylate, syndiotactic polystyrene and polyethylene can be effectively promoted, so that the secondary modification treatment of the organosilicon modified epoxy resin is realized, and the low-temperature resistant hot melt adhesive provided by the invention still has the tensile property of 250-260% at the temperature of-50 ℃.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.