阅读说明：本技术 一种高表面亲水性聚丙烯复合材料及其制备方法和应用 (High-surface-hydrophilicity polypropylene composite material and preparation method and application thereof ) 是由 杨友强 丁超 陈平绪 程文建 简思强 许齐勇 李振华 魏金刚 余小鸽 戴剑 夏超 于 2021-07-22 设计创作，主要内容包括：本发明提供了一种高表面亲水性聚丙烯复合材料及其制备方法和应用,所述复合材料包括如下按重量份计算的组分：聚丙烯树脂55～85份；玻璃纤维10～40份；第一亲水改性剂1～20份；第二亲水改性剂大于0小于等于5份；其它功能助剂0～7份；所述第一亲水改性剂的重均分子量为50000～200000的含羧基、羟基、酰胺基或酯基的聚合物；所述第二亲水改性剂为重均分子量为500～10000的含羧基、羟基、酰胺基或酯基的C5～C50烷基寡聚物。所述复合材料通过第一亲水改性剂和第二亲水改性剂的协同作用,使得能够满足制备塑料手模,且成品率和寿命得到大幅度提高,手套成品率大于等于97％,使用寿命达到2年以上。(The invention provides a high-surface-hydrophilicity polypropylene composite material, a preparation method and an application thereof, wherein the composite material comprises the following components in parts by weight: 55-85 parts of polypropylene resin; 10-40 parts of glass fiber; 1-20 parts of a first hydrophilic modifier; the second hydrophilic modifier is more than 0 and less than or equal to 5 parts; 0-7 parts of other functional additives; the first hydrophilic modifier is a polymer containing carboxyl, hydroxyl, amide or ester groups, and the weight-average molecular weight of the first hydrophilic modifier is 50000-200000; the second hydrophilic modifier is C5-C50 alkyl oligomer which has the weight-average molecular weight of 500-10000 and contains carboxyl, hydroxyl, amido or ester groups. The composite material can meet the requirement of preparing a plastic hand mold through the synergistic effect of the first hydrophilic modifier and the second hydrophilic modifier, the yield and the service life of the composite material are greatly improved, the glove yield is more than or equal to 97%, and the service life of the composite material reaches more than 2 years.)

1. The polypropylene composite material with high surface hydrophilicity is characterized by comprising the following components in parts by weight:

the first hydrophilic modifier is a polymer containing carboxyl, hydroxyl, amide or ester groups, and the weight-average molecular weight of the first hydrophilic modifier is 50000-200000;

the second hydrophilic modifier is C5-C50 alkyl oligomer which has the weight-average molecular weight of 500-10000 and contains carboxyl, hydroxyl, amido or ester groups.

2. The polypropylene composite material with high surface hydrophilicity according to claim 1, is characterized by comprising the following components in parts by weight:

3. the polypropylene composite material with high surface hydrophilicity as claimed in claim 1 or 2, wherein the first hydrophilic modifier has a weight average molecular weight of 100000-150000.

4. The polypropylene composite material with high surface hydrophilicity as claimed in claim 1 or 2, wherein the second hydrophilic modifier has a weight average molecular weight of 1000 to 5000.

5. The polypropylene composite material with high surface hydrophilicity as claimed in claim 1, wherein the glass fiber has a retention length of 0.1 to 1 mm.

6. The polypropylene composite material with high surface hydrophilicity as claimed in claim 1, wherein the other functional auxiliary agent is one or more of a graft compatilizer, an antioxidant or a lubricant.

7. The preparation method of the polypropylene composite material with high surface hydrophilicity as claimed in any one of claims 1 to 6, characterized by comprising the following steps:

s1, weighing polypropylene resin, glass fiber, a first hydrophilic modifier, a second hydrophilic modifier and other functional auxiliaries according to a proportion, and blending uniformly to obtain a premix;

s2, carrying out melt extrusion and granulation on the premix obtained in the step S2 to obtain the high-surface-hydrophilicity polypropylene composite material.

8. Use of the polypropylene composite material with high surface hydrophilicity as defined in any one of claims 1 to 6 for preparing plastic products.

9. A plastic hand mold, which is made of a polypropylene composite material having a high surface hydrophilicity according to any one of claims 1 to 6.

10. The method for preparing a plastic hand mold according to claim 9, wherein the plastic hand mold is prepared by a blow molding or injection molding method.

Technical Field

The invention relates to the technical field of high polymer plastics, and particularly relates to a high-surface-hydrophilicity polypropylene composite material and a preparation method and application thereof.

Background

The glove mold is a special mold for dipping and forming gloves in rubber, latex and PVC glove industry production. Before use, the glove model is cleaned by acid liquor, heated by hot water, dipped in a coagulant and dried, then dipped in molten rubber or latex, dried in an oven after dipping, added with a fiber inner sleeve and heated by hot water, and finally vulcanized in the oven and dried to form. In the whole process, the glove mold is subjected to repeated rapid cooling, rapid heating and chemical corrosion, and the glove mold is required to have good corrosion resistance and thermal stability, so that the ceramic hand mold is used in the glove industry and has good heat resistance, acid resistance, alkali resistance and corrosion resistance.

However, the ceramic hand mold has the defects of large specific gravity (high production energy consumption), fragility, short service life, incapability of recycling (poor environmental protection property) and the like, and the ceramic hand mold produced by the prior art has the online service life of generally 6 months in the production of nitrile rubber gloves.

Therefore, for the reasons mentioned above, researchers are also looking for a method to replace the ceramic hand mold, for example, chinese patent (CN107053564A) discloses a method for manufacturing a plastic hand mold, but fluoroplastics are used as raw materials, and the fluoroplastics have poor hydrophilic performance, which may result in the defects of short service life and low qualified rate of glove products.

Therefore, there is a need for a new composite material for use in the manufacture of hand molds that provides long service life and high glove article qualification.

Disclosure of Invention

The invention provides a polypropylene composite material with high surface hydrophilicity, which aims to overcome the defects of short service life of the plastic hand mold and low glove yield.

The invention also aims to provide a preparation method of the polypropylene composite material with high surface hydrophilicity.

Another object of the present invention is to provide the use of the polypropylene composite material with high surface hydrophilicity.

In order to achieve the purpose, the invention adopts the technical scheme that:

a high-surface-hydrophilicity polypropylene composite material comprises the following components in parts by weight:

the first hydrophilic modifier is a polymer containing carboxyl, hydroxyl, amide or ester groups, and the weight-average molecular weight of the first hydrophilic modifier is 50000-200000;

the second hydrophilic modifier is C5-C50 alkyl oligomer which has the weight-average molecular weight of 500-10000 and contains carboxyl, hydroxyl, amido or ester groups.

The inventor finds that the polypropylene resin has the advantages of light specific gravity, excellent acid and alkali resistance and the like, but the polypropylene is a typical hydrophobic material, the water contact angle is larger than 90 degrees, and the hydrophilic property of the polypropylene is required to be improved if the polypropylene is applied to the preparation of hand models, so the inventor adopts a first hydrophilic modifier and a second hydrophilic modifier to form a synergistic effect on the polypropylene resin, the first hydrophilic modifier is a macromolecular hydrophilic modifier and is mainly distributed in a polypropylene resin matrix to improve the molecular polarity of the polypropylene resin, thereby improving the overall hydrophilic capability of the material; and the second hydrophilic modifier is used as a micromolecular hydrophilic modifier to directly improve the hydrophilic capacity of the surface of the polypropylene resin, so that the hydrophilic capacity of the polypropylene resin is improved.

In addition, the first hydrophilic modifier is slowly migrated to the surface of the polypropylene resin, so that the service life of the hand mold can be greatly prolonged to 2 years.

Further, the finding that when the content of the second hydrophilic modifier is less than or equal to 5 parts, the gum dipping amount can be controlled within 0.04-0.08 mm of the thickness of the glove product during the preparation of the glove product, the glove yield is high, and if the addition amount is too high, the gum dipping amount is too much, the uniformity is reduced, and the yield is reduced.

When the content of the first hydrophilic modifier is less than 1 part, the hydrophilic performance cannot be achieved, and after the content of the first hydrophilic modifier exceeds 20 parts, the impact strength and the tensile strength of the material are sharply reduced, so that the material cannot be used for preparing polypropylene hand molds.

Preferably, the polypropylene composite material with high surface hydrophilicity comprises the following components in parts by weight:

when the glass fiber is 15-25, the rigidity and toughness effect is better; when the first hydrophilic modifier is 5-15 parts, the surface hydrophilicity uniformity and the mechanical property are good; when the content of the second hydrophilic modifier is less than 0.5, the hydrophilic wettability effect of the surface is slow in the use process, and when the addition amount exceeds 2 parts, the second hydrophilic modifier is easy to migrate to the surface, so that the yield is reduced.

Preferably, the first hydrophilic modifier has a weight average molecular weight of 100000 to 150000, and has a good effect when the weight average molecular weight is 50000 to 150000.

Preferably, the weight average molecular weight of the second hydrophilic modifier is 1000-5000, when the molecular weight is too low, the migration efficiency is too fast, so that the long-acting property of the hydrophilic effect is insufficient, and when the molecular weight is too high, the migration efficiency is too slow, so that the hydrophilic effect is insufficient.

More preferably, the first hydrophilic modifier is one or more of polyetheramide, ethylene acrylic acid copolymer, polyether polyol, ethylene-vinyl acetate copolymer, or polyamide.

When the first hydrophilic modifier is one or more of polyether amide, ethylene acrylic acid copolymer, polyether glycol, ethylene-vinyl acetate copolymer or polyamide, the molecular structure of the first hydrophilic modifier is provided with strong polar hydrophilic groups, so that the polarity of the polypropylene material can be obviously improved, and the hydrophilic performance is improved.

More preferably, the second hydrophilic modifier is one or more of polyethylene glycol octyl phenyl ether, hydroxyl terminated stearamide, erucamide or pentaerythritol stearate.

Preferably, the retention length of the glass fiber is 0.1-1 mm.

When the retention length of the glass fiber is within the range of 0.1-1 mm, the material has good strength and appearance performance, the retention length of the glass fiber is too short, the strength of the material is low, the retention length of the glass fiber is too long, and the material is easy to have appearance defects such as floating fibers.

The initial length of the glass fiber is 2-10 mm.

Preferably, the polypropylene resin is one or both of homo-polypropylene and co-polypropylene.

Preferably, the other functional auxiliary agents are one or more of graft compatilizer, antioxidant and lubricant.

The graft compatilizer is added into the system, so that the compatibility of the composite material is better, the antioxidant is added into the composite material to have an antioxidant effect, and the lubricating effect is better when the lubricant is added.

The content of the grafting compatilizer is 0-5 parts, and the grafting compatilizer is a graft polymer of polar monomers and polypropylene, wherein the polar monomers are selected from one or more of maleic anhydride, acrylic acid or acrylate derivatives.

The grafted compatilizer can effectively improve the compatibility between polypropylene and glass fiber and improve the appearance and mechanical property of the material.

The antioxidant comprises 0-1 part of antioxidant, and the antioxidant comprises one or more of hindered amine antioxidant, hindered phenol antioxidant, phosphite antioxidant, calixarene antioxidant or thioester antioxidant.

The lubricant comprises 0-1 part of lubricant, and the lubricant comprises one or more of amide lubricant, metal soap lubricant or low molecular ester lubricant.

The preparation method of the high-surface-hydrophilicity polypropylene composite material comprises the following steps:

s1, weighing polypropylene resin, glass fiber, a first hydrophilic modifier, a second hydrophilic modifier and other functional auxiliaries according to a proportion, and blending uniformly to obtain a premix;

s2, carrying out melt extrusion and granulation on the premix obtained in the step S2 to obtain the high-surface-hydrophilicity polypropylene composite material.

A plastic hand mold is made of the polypropylene composite material with high surface hydrophilicity.

The plastic hand mold made of the polypropylene composite material with high surface hydrophilicity has high yield and long service life.

The preparation method of the plastic hand mold is prepared by a blow molding or injection molding method.

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

the invention provides a high-surface-hydrophilicity polypropylene composite material, which has heat resistance and solvent resistance, and the inventor finds that the synergistic effect of a first hydrophilic modifier and a second hydrophilic modifier can meet the requirement of preparing a plastic hand mold, the glove yield and the service life of the hand mold are greatly improved, the glove yield is more than or equal to 97%, and the service life is more than 2 years.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.

The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.

The following examples and comparative examples employ the following starting materials:

polypropylene resin: china petrochemical group corporation;

glass fiber: fiber length 3mm, retention length 0.25 mm: china giant stone corporation;

first hydrophilic modifier a: polyetheramides, weight average molecular weight 50000, abcoma, france;

first hydrophilic modifier B: polyetheramides, weight-average molecular weight 100000, abcoma, france;

first hydrophilic modifier C: polyetheramides, weight average molecular weight 200000, abcoma france;

first hydrophilic modifier D: polyamide, weight average molecular weight 150000, maedia polyamide, inc. of new meeting, guangdong;

first hydrophilic modifier E: ethylene-acrylic acid copolymer, weight average molecular weight 300000, dow chemical;

first hydrophilic modifier F: polyether polyol, weight average molecular weight 20000, Dow chemical;

second hydrophilic modifier a: hydroxyl-terminated stearamide with the weight-average molecular weight of 500, and the golden hair technology;

second hydrophilic modifier B: hydroxyl-terminated stearamide, weight average molecular weight 2000, golden hair technology;

second hydrophilic modifier C: hydroxyl-terminated stearamide, with the weight-average molecular weight of 10000, and the technology of golden hair;

second hydrophilic modifier D: erucamide, weight average molecular weight 1000, sitaxacum chemical;

second hydrophilic modifier E: pentaerythritol stearate, weight average molecular weight 5000, german corning;

second hydrophilic modifier F: polyethylene glycol octyl phenyl ether, weight average molecular weight 20000, dow chemical;

grafting compatilizer: good easy compatilizer Jiangsu GmbH;

lubricant: zhongshan Huaming Tai chemical Co., Ltd;

antioxidant: tianjin Lianlong New Material Ltd.

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

The high surface hydrophilicity polypropylene composite material is prepared by the following method in each embodiment and comparative example of the invention, and comprises the following steps:

s1, weighing polypropylene resin, glass fiber, a first hydrophilic modifier, a second hydrophilic modifier and other functional auxiliaries according to a proportion, and blending uniformly to obtain a premix;

s2, carrying out melt extrusion and granulation on the premix obtained in the step S2 to obtain the high-surface-hydrophilicity polypropylene composite material, wherein the extrusion processing temperature is 180-220 ℃.

Examples 1 to 12

The embodiment provides a series of high surface hydrophilicity polypropylene composite materials, and the specific formula is shown in table 1;

TABLE 1 formulations (parts) of examples 1 to 12

Examples 13 to 19

The embodiment provides a series of high surface hydrophilicity polypropylene composite materials, and the specific formula is shown in table 2;

TABLE 2 formulations (parts) of examples 13 to 19

Comparative examples 1 to 7

Comparative examples a series of polypropylene composites were provided, the specific formulations are given in table 3;

TABLE 3 formulations (parts) of comparative examples 1 to 7

The injection molding method of the polypropylene composite material of the above examples and comparative examples is used for preparing the plastic hand mold, and comprises the following steps:

n1. drying the polypropylene composite materials with high surface hydrophilicity of the examples and the comparative examples, and injection molding the left and the right single-side parts by an injection molding machine;

and N2, bonding the left single-sided piece and the right single-sided piece to obtain a complete plastic hand mold product.

The composites of the above examples and comparative examples, or hand molds made from the above composites, were tested by the following performance test methods:

hydrophilicity of the composite material: according to ISO 8296: and (2006-9) according to a standard method, the hydrophilicity of the material is characterized by adopting a dyne index, and the higher the dyne index is, the better the hydrophilicity is.

Glove yield: and (4) carrying out testing by adopting a water hanging method, and counting the rate of liquid leakage of the water hanging test of 30000 gloves.

Service life: the service life of the hand model is evaluated by adopting a continuous operation method, the time of operating once according to a standard butyronitrile glove production process is about 1h, the operation is continued for 17520 times (corresponding to 2 years), the hand model is observed every 720h (corresponding to 1 month), whether the hand model has phenomena of embrittlement, pits, rough surface and the like in the operation process is evaluated, whether the yield of the glove is obviously reduced (the yield is reduced by more than 5 percent compared with the normal yield) is recorded, when the hand model has obvious defects or the yield of the glove is obviously reduced, the hand model cannot be used continuously, and the time at the moment is recorded as the service life.

Heat resistance: and (3) placing the hand model in a 120 ℃ oven to bake for 8h, evaluating the deformation or softening condition of the hand model, wherein the hand model cannot be obviously deformed or softened after being baked, and the hand model can pass through the oven without obvious deformation or softening.

Solvent resistance: the hand mold is firstly placed in 5% nitric acid solution for soaking for a week and then placed in 5% sodium hydroxide solution for soaking for a week, the hand mold is taken out for observation, and after being soaked in acid and alkali, the hand mold cannot have the phenomena of embrittlement, pits, rough surface and the like, and the hand mold can pass the phenomena without the phenomena.

TABLE 4 data for examples and comparative examples

From examples 1 to 5, when the content of the second hydrophilic modifier is 0.5 to 2 parts, the effects of hydrophilicity and yield are good; in examples 6 to 9, the hydrophilicity and yield were increased with the increase in the content of the first hydrophilic modifier, but the mechanical properties were decreased with the increase in the first hydrophilic agent, and therefore, the overall effect was good when the content of the first hydrophilic agent was 5 to 15. See from examples 13 to 15. The first hydrophilic modifier has a better effect when the weight average molecular weight is 50000-150000.

From comparative examples 1 and 2, the yield and service life of the hydrophilic modifier used were greatly reduced; in the view of comparative examples 3 and 4, comparative example 3 is that the content of the second hydrophilic modifier is too high, the high yield and the extension of the service life cannot be achieved; comparative example 4 the mechanical properties were drastically reduced due to the excessively high content of the first hydrophilic modifier, and the hand mold could not be prepared and the related properties could not be tested.

The first hydrophilic modifier in comparative example 5 had too large a weight average molecular weight and could not satisfy the service life; the second hydrophilic modifier in comparative example 6 has an excessively large weight average molecular weight, resulting in a decrease in hydrophilic ability and unsatisfactory yield and service life.

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.