CN114591515A - Polyolefin polymer aqueous emulsion and preparation method and application thereof - Google Patents

Polyolefin polymer aqueous emulsion and preparation method and application thereof Download PDF

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CN114591515A
CN114591515A CN202210211715.6A CN202210211715A CN114591515A CN 114591515 A CN114591515 A CN 114591515A CN 202210211715 A CN202210211715 A CN 202210211715A CN 114591515 A CN114591515 A CN 114591515A
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polyolefin polymer
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曹均凯
龙浩
郝名扬
韦联川
胡颜刚
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Chongqing Polycomp International Corp
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03C25/10—Coating
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    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
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    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract

A process for preparing the aqueous emulsion of polyolefine polymer features that if the weight-average molecular weight of polyolefine polymer is greater than 20000, the grafted polyolefine polymer has better flowability without breaking the molecular chain of polymer, and the original structure of grafted polyolefine polymer is retained in the aqueous emulsion. Namely, the invention can complete the preparation of random copolymerization, isotactic copolymerization, syndiotactic copolymerization and graft polyolefin polymer emulsion on the premise of not using organic solvent. The polyolefin polymer aqueous emulsion is used as a glass fiber impregnating compound to further reinforce a polyolefin composite base material, so that the molecular chain structure of the grafted polyolefin polymer has good consistency with the reinforced base material according to a similar compatibility principle, and further good mechanical properties are obtained.

Description

Polyolefin polymer water-based emulsion and preparation method and application thereof
Technical Field
The invention relates to the technical field of glass fiber twisted yarn production, in particular to a polyolefin polymer aqueous emulsion and a preparation method and application thereof.
Background
Various artificial polymers have been widely used in the field of glass fiber reinforced composites in order for the glass fiber reinforced composites to be able to obtain the special properties of the artificial polymer materials, such as excellent mechanical properties, etc. In particular, when the glass fiber is used for reinforcing polyolefin polymer materials, the polyolefin polymer emulsion is used for treating the surface of the glass fiber, so that special surface protection can be provided for the glass fiber, and the adhesion between the glass fiber and a substrate can be improved. In order to provide superior compatibility of the glass fibers with the polyolefin polymer substrate, the surface of the glass fibers is typically treated with a polyolefin treating agent that is the same as or similar to the polyolefin polymer substrate being reinforced.
If the weight average molecular weight of the polyolefin polymer is less than 10000, the polyolefin polymer can be easily emulsified under proper stirring after adding the emulsifier, and an emulsion with a corresponding concentration can be obtained by adding a proper amount of water into the emulsification system. However, when the weight average molecular weight of the polyolefin polymer is more than 10000, emulsification becomes difficult because the polyolefin polymer has poor fluidity when melted, and it is difficult to prepare a corresponding emulsion. Moreover, the isotactic and syndiotactic polyolefin polymers have a high degree of crystallinity on cooling, which makes the emulsification process more complicated and even difficult. The polyolefin polymers generally used for emulsification are mostly random copolymerized or amorphous polyolefin polymers due to the influence of crystallinity. For the polyolefin polymer having high crystallinity, isotactic and random copolymerized polyolefin polymers may be mixed and melted in a certain ratio and then an emulsion may be prepared. However, in this method, the proportion of the isotactic copolymerized polyolefin polymer must be less than 30%. In order to obtain an isotactic copolymerized polyolefin polymer emulsion with high molecular weight, the polyolefin polymer can be dissolved in a heated organic solvent, and then an auxiliary agent is added for emulsification, but the process needs to remove the organic solvent in a later stage by extraction or drying, and the steps are complex and tedious.
Furthermore, in some aqueous polyolefin polymer emulsion formulations it is necessary to add additional amounts of co-emulsifiers, some up to 30% relative to dry matter, which may be non-ionic, cationic, anionic, such as: span 80, span 60, tween 80, cetyl trimethyl ammonium bromide, fatty alcohol-polyoxyethylene ether sulfate, fatty alcohol-polyoxyethylene ether phosphate and the like, which are required to be searched and tried in practice to obtain the emulsion with better stability.
Disclosure of Invention
The invention provides a preparation method and application of polyolefin polymer water-based emulsion, which can complete the preparation of random copolymerization, isotactic copolymerization, syndiotactic copolymerization and grafted polyolefin polymer emulsion on the premise of not using organic solvent for grafted polyolefin polymer with the weight-average molecular weight of more than 20000. After the impregnating compound prepared by the polyolefin polymer water-based emulsion is used for treating the surface of glass fiber, the impregnating compound can be well used for reinforcing a polyolefin polymer base material.
The technical scheme of the invention is as follows:
an aqueous polyolefin polymer emulsion comprising 15 to 25 parts by mass of a grafted polyolefin polymer, 3 to 10 parts by mass of a fatty acid, 1 to 5 parts by mass of an inorganic base, 2 to 7 parts by mass of an organic base and 55 to 76 parts by mass of water; wherein the weight average molecular weight of the grafted polyolefin polymer is greater than 20000.
Preferably, the grafted polyolefin-based polymer comprises one or more of a polyolefin blend of C2-C4, a polypropylene grafted acid, and a polypropylene grafted anhydride.
Preferably, the polyolefin blend of C2 to C4 comprises one or more of polyethylene, polyethylene-polypropylene copolymer, isotactic polypropylene, random copolymer polypropylene, polybutadiene and polyisobutylene; or the polypropylene grafted acid comprises one or more of acrylic acid, methacrylic acid, methacrylate ester and acrylate ester; and/or the polypropylene grafted anhydride comprises one or more of maleic anhydride, acrylic anhydride, and methacrylic anhydride.
Preferably, the fatty acid comprises a saturated fatty acid, and the saturated fatty acid comprises one or more of behenic acid, stearic acid, lauric acid, myristic acid, caprylic acid succinate, capric acid, palmitic acid and arachidic acid.
Preferably, the fatty acid comprises an unsaturated fatty acid comprising one or more of oleic acid, linoleic acid, linolenic acid and arachidonic acid.
Preferably, the inorganic base comprises one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
Preferably, the organic base comprises one or more of ethanolamine, ethylenediamine, dimethylamine, isopropylamine, triethanolamine, tert-butylamine, octylamine, benzylamine, hexamethylenetetramine, o-aminophenol, o-toluidine, 8-hydroxyquinoline and diphenylamine.
The preparation method of the polyolefin polymer aqueous emulsion comprises the following steps:
s1, mixing 15-25 parts by mass of a grafted polyolefin polymer, 3-10 parts by mass of fatty acid and 1-5 parts by mass of inorganic base, and fully melting and uniformly stirring at a temperature higher than the melting point of the grafted polyolefin polymer; obtaining a component 1;
s2, adding 2-7 parts by mass of organic base and 10-20 parts by mass of water mixture into the component 1 to obtain a component 2;
s3, stirring the component 2 at a temperature higher than the melting point of the grafted polyolefin polymer, adding 45-60 parts by mass of water, adjusting the solid content to be 30-40%, fully stirring, cooling to a temperature below the melting point, and thus obtaining the polyolefin polymer aqueous emulsion.
A glass fiber sizing agent comprises 0.5-5 parts by mass of a coupling agent, 1-4 parts by mass of a lubricant, 1-10 parts by mass of an auxiliary film forming agent, 1-3 parts by mass of an antistatic agent, 100-400 parts by mass of water and 30-50 parts by mass of a polyolefin polymer aqueous emulsion prepared by the method. Preferably, the coupling agent comprises an amine-based silane coupling agent; and/or the lubricant comprises a cationic lubricant or a nonionic lubricant; and/or the particle size of the polyolefin polymer aqueous emulsion is 150nm-400 nm.
Compared with the prior art, the invention has the advantages that:
1. the invention relates to a polyolefin polymer water-based emulsion, a preparation method and application thereof, wherein when the weight average molecular weight of the polyolefin polymer is larger than 20000, the grafted polyolefin polymer can have good fluidity without breaking the molecular chain of the polymer only by adding a proper amount of fatty acid and inorganic base, and the grafted polyolefin polymer can form the water-based emulsion, and meanwhile, the original structure of the grafted polyolefin polymer material can be kept in the water-based emulsion. When the polyolefin polymer aqueous emulsion is used as a glass fiber impregnating compound to further reinforce the base material, the molecular chain structure of the grafted polyolefin polymer is enabled to have good consistency with the reinforced base material according to the similar compatibility principle, and the reinforced polyolefin composite material base material is enabled to have good mechanical property.
2. When the polyolefin polymer aqueous emulsion is used as a sizing agent for treating glass fibers, fatty acid contained in the grafted polyolefin polymer aqueous emulsion is not required to be removed, and the fatty acid can be used as a lubricant, so that the addition of an additional lubricant in the sizing agent is avoided. Meanwhile, acid in the grafted polyolefin polymer can be neutralized by organic base and/or inorganic base, so that the particle size distribution stability of the product is effectively improved.
3. The polyolefin polymer aqueous emulsion does not use an emulsifier, but a large amount of products similar to anionic surfactants are generated by the saponification of neutralized fatty acid, and the products can play the role of the emulsifier.
Detailed Description
In order to facilitate an understanding of the invention, the invention is described in more detail below with reference to specific examples.
Example 1
An aqueous polyolefin polymer emulsion 1 includes 100 parts of a grafted polyolefin polymer, 20 parts of stearic acid, 8 parts of potassium hydroxide, 15 parts of isopropylamine and 330 parts of deionized water. Wherein the grafted polyolefin polymer is a polypropylene-maleic anhydride graft copolymer (FH118, Niwable's optical New Material science and technology Co., Ltd.) having a weight average molecular weight of 75000, in which the maleic anhydride grafting rate is 0.7%.
The preparation method of the polyolefin polymer water-based emulsion 1 comprises the following steps:
s1, weighing 100 parts of grafted polyolefin polymer, 20 parts of stearic acid, 8 parts of potassium hydroxide, 15 parts of isopropylamine and 330 parts of deionized water according to parts by mass. Mixing 100 parts of grafted polyolefin polymer, 25 parts of stearic acid and 8 parts of potassium hydroxide, putting into a pressure kettle, heating to 175 ℃, keeping the temperature for 15 minutes, and stirring at a low speed to obtain a component 1; wherein, the low-speed stirring adopts a planetary stirrer, and the scraping rotating speed is about 300 rpm;
s2, injecting 15 parts of isopropylamine and 120 parts of deionized water into the component 1 by using a pressure pump, wherein the water temperature is about 95 ℃, and stirring at a high speed for 30 minutes when the temperature of the pressure kettle is raised to 175 ℃ to obtain a component 2; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
S3, injecting 210 parts of deionized water into the component 2 system by using a pressure pump, keeping the high-speed stirring for 15 minutes when the temperature of the pressure kettle is raised to 175 ℃ and then rapidly cooling to 40 ℃ to obtain a polyolefin polymer emulsion 1 with the solid content of 30 percent, wherein the water temperature is about 95 ℃; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
Example 2
An aqueous polyolefin polymer emulsion 2 comprises 100 parts of a grafted polyolefin polymer, 20 parts of stearic acid, 8 parts of potassium hydroxide, 15 parts of isopropylamine and 330 parts of deionized water. Wherein the grafted polyolefin polymer is a polypropylene-maleic anhydride graft copolymer (FH1016, Niwable's opto-new materials science and technology Co., Ltd.) having a weight average molecular weight of 50000, in which the maleic anhydride grafting rate is 1.0%.
The preparation method of the polyolefin polymer water-based emulsion 2 comprises the following steps:
s1, taking 100 parts of grafted polyolefin polymer, 20 parts of stearic acid, 8 parts of potassium hydroxide, 15 parts of isopropylamine and 345 parts of deionized water according to parts by mass; mixing 100 parts of grafted polyolefin polymer, 20 parts of stearic acid and 8 parts of potassium hydroxide, putting into a pressure kettle, heating to 165 ℃, starting low-speed stirring and mixing for 15 minutes to obtain a component 1; wherein, the low-speed stirring adopts a planetary stirrer, and the scraping rotating speed is about 300 rpm;
s2, injecting 15 parts of isopropylamine and 120 parts of deionized water into the component 1 by using a pressure pump, and stirring at a high speed for 30 minutes to obtain a component 2 when the temperature of the pressure kettle is raised to 165 ℃ at about 95 ℃; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
S3, injecting 210 parts of deionized water into the component 2 system by using a pressure pump, keeping the high-speed stirring for 15 minutes when the temperature of the pressure kettle is raised to 165 ℃ and then rapidly cooling to 40 ℃ to obtain polyolefin polymer emulsion 2 with the solid content of 30 percent, wherein the water temperature is about 95 ℃; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
Example 3
An aqueous emulsion 3 of polyolefin polymer comprises 100 parts of grafted polyolefin polymer, 20 parts of stearic acid, 8 parts of potassium hydroxide, 15 parts of isopropylamine and 360 parts of deionized water, and 8 parts of
Figure BDA0003531635240000041
G800K (C16-18 alcohol polyoxyethylene ether 80EO, Saxol chemical, China Co., Ltd.) and 5 parts
Figure BDA0003531635240000042
315 (isomeric tridecanol polyoxyethylene ether 1.5EO, Soxhlet chemical, China Co., Ltd.). Wherein the grafted polyolefin polymer is a polypropylene-maleic anhydride graft copolymer (FH118, Niwable's optical New Material science and technology Co., Ltd.) having a weight average molecular weight of 75000, in which the maleic anhydride grafting rate is 0.7%.
The preparation method of the polyolefin polymer water-based emulsion 3 comprises the following steps:
s1, weighing 100 parts of grafted polyolefin polymer, 20 parts of stearic acid, 8 parts of potassium hydroxide, 15 parts of isopropylamine and 8 parts of
Figure BDA0003531635240000051
G800K, 5 parts
Figure BDA0003531635240000052
315 and 360 parts of deionized water; 100 parts of grafted polyolefin polymer, 20 parts of stearic acid, 8 parts of potassium hydroxide and 8 parts of
Figure BDA0003531635240000053
G800K and 5 parts
Figure BDA0003531635240000054
315, putting the mixture into a pressure kettle, heating the mixture to 175 ℃, preserving the heat for 15 minutes and keeping stirring at a low speed to obtain a component 1; wherein, the low-speed stirring adopts a planetary stirrer, and the scraping rotating speed is about 300 rpm;
s2, injecting 15 parts of isopropylamine and 120 parts of deionized water into the component 1 by using a pressure pump, wherein the water temperature is about 95 ℃, and stirring at a high speed for 30 minutes when the temperature of the pressure kettle is raised to 175 ℃ to obtain a component 2; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
S3, injecting 240 parts of deionized water into the component 2 system by using a pressure pump, keeping the high-speed stirring for 15 minutes when the temperature of the pressure kettle is raised to 175 ℃ and then rapidly cooling to 40 ℃ to obtain the polyolefin polymer emulsion with the solid content of 30 percent, wherein the water temperature is about 95 ℃. Wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
Example 4
An aqueous polyolefin polymer emulsion 4 comprises 100 parts of a grafted polyolefin polymer, 35 parts of stearic acid, 10 parts of potassium hydroxide, 15 parts of isopropylamine and 350 parts of deionized water. Wherein the grafted polyolefin polymer is a polypropylene-maleic anhydride graft copolymer (FH1016, Niwable's opto-new materials science and technology Co., Ltd.) having a weight average molecular weight of 50000, in which the maleic anhydride grafting rate is 1.0%.
The preparation method of the polyolefin polymer water-based emulsion 2 comprises the following steps:
s1, taking 100 parts of grafted polyolefin polymer, 35 parts of stearic acid, 10 parts of potassium hydroxide, 15 parts of isopropylamine and 350 parts of deionized water in parts by mass; mixing 100 parts of grafted polyolefin polymer, 35 parts of stearic acid and 10 parts of potassium hydroxide, putting into a pressure kettle, heating to 165 ℃, starting low-speed stirring and mixing for 15 minutes to obtain a component 1; wherein, the low-speed stirring adopts a planetary stirrer, and the scraping rotating speed is about 300 rpm;
s2, injecting 15 parts of isopropylamine and 120 parts of deionized water into the component 1 by using a pressure pump, wherein the water temperature is about 95 ℃, and stirring at a high speed for 30 minutes when the temperature of the pressure kettle is raised to 165 ℃ to obtain a component 2; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
S3, injecting 230 parts of deionized water into the component 2 system by using a pressure pump, keeping the high-speed stirring for 15 minutes when the temperature of the pressure kettle is raised to 165 ℃ and then rapidly cooling to 40 ℃ to obtain polyolefin polymer emulsion 2 with the solid content of 30 percent, wherein the water temperature is about 95 ℃; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
Example 5
An aqueous emulsion 5 of polyolefin polymer comprises 100 parts of grafted polyolefin polymer, 10 parts of stearic acid and 4 parts of hydrogenPotassium oxide, 15 parts of isopropylamine and 366 parts of deionized water, 18 parts
Figure BDA0003531635240000055
G800K (C16-18 alcohol polyoxyethylene ether 80EO, Saxol chemical, China Co., Ltd.) and 10 parts of
Figure BDA0003531635240000056
315 (isomeric tridecanol polyoxyethylene ether 1.5EO, Soxhlet chemical, China Co., Ltd.). Wherein the grafted polyolefin polymer is a polypropylene-maleic anhydride graft copolymer (FH1016, Niwable's opto-new materials science and technology Co., Ltd.) having a weight average molecular weight of 50000, in which the maleic anhydride grafting rate is 1.0%.
The preparation method of the polyolefin polymer water-based emulsion 2 comprises the following steps:
s1, weighing 100 parts of grafted polyolefin polymer, 10 parts of stearic acid, 4 parts of potassium hydroxide, 15 parts of isopropylamine and 18 parts of
Figure BDA0003531635240000061
G800K, 10 parts
Figure BDA0003531635240000062
315 and 366 parts of deionized water; 100 parts of grafted polyolefin polymer, 10 parts of stearic acid and 18 parts of
Figure BDA0003531635240000063
G800K, 10 parts
Figure BDA0003531635240000064
315 and 4 parts of potassium hydroxide are mixed and then put into a pressure kettle, after the temperature is raised to 165 ℃, the mixture is stirred and mixed for 15 minutes at a low speed, and a component 1 is obtained; wherein, the low-speed stirring adopts a planetary stirrer, and the scraping rotating speed is about 300 rpm;
s2, injecting 15 parts of isopropylamine and 120 parts of deionized water into the component 1 by using a pressure pump, wherein the water temperature is about 95 ℃, and stirring at a high speed for 30 minutes when the temperature of the pressure kettle is raised to 165 ℃ to obtain a component 2; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
S3, injecting 244 parts of deionized water into the component 2 system by using a pressure pump, keeping stirring at a high speed for 15 minutes when the temperature of the pressure kettle is raised to 165 ℃ and then quickly cooling to 40 ℃ to obtain polyolefin polymer emulsion 2 with the solid content of 30 percent, wherein the water temperature is about 95 ℃; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
Comparative example 1
A polyolefin polymer emulsion 1 comprises 100 parts of a grafted polyolefin polymer, 15 parts of isopropylamine and 18 parts of
Figure BDA0003531635240000065
G800K (C16-18 alcohol polyoxyethylene ether 80EO, Saxol chemical China Co., Ltd.) and 10 parts of
Figure BDA0003531635240000066
315 (isomeric tridecanol polyoxyethylene ether 1.5EO, Soxhlet chemical, China Co., Ltd.) and 375 parts of deionized water. Wherein the grafted polyolefin polymer is a polypropylene-maleic anhydride graft copolymer (FH118, Niwable optical New Material science and technology Co., Ltd.) having a weight average molecular weight of 75000, wherein the maleic anhydride grafting ratio is 0.7%
The preparation method of the polyolefin polymer water-based emulsion comparative example 1 comprises the following steps:
s1, weighing 100 parts of grafted polyolefin polymer, 15 parts of isopropylamine and 30 parts of
Figure BDA0003531635240000067
Figure BDA0003531635240000068
G800K, 10 parts
Figure BDA0003531635240000069
315 and 375 parts deionized water; 100 parts of grafted polyolefin polymer and 30 parts of
Figure BDA00035316352400000610
G800K and 10 parts
Figure BDA00035316352400000611
315, putting the mixture into a pressure kettle, heating the mixture to 175 ℃, preserving the heat for 15 minutes and keeping stirring at a low speed to obtain a component 1; wherein, the low-speed stirring adopts a planetary stirrer, and the scraping rotating speed is about 300 rpm;
s2, injecting 15 parts of isopropylamine and 120 parts of deionized water into the component 1 by using a pressure pump, wherein the water temperature is about 95 ℃, and stirring at a high speed for 30 minutes when the temperature of the pressure kettle is raised to 175 ℃ to obtain a component 2; wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
S3, injecting 255 parts of deionized water into the component 2 system by using a pressure pump, keeping the high-speed stirring for 15 minutes when the temperature of the pressure kettle is raised to 175 ℃ and then rapidly cooling to 40 ℃ to obtain the polyolefin polymer emulsion with the solid content of 30 percent, wherein the water temperature is about 95 ℃. Wherein, the high-speed stirring adopts a shearing stirrer, and the rotating speed is 2000 rpm.
Table 1 ingredient ratio table of each example and comparative example
Figure BDA0003531635240000071
TABLE 2 particle size and demixing time after standing comparison table of emulsions obtained in examples and comparative examples
Example 1 Practice ofExample 2 Example 3 Example 4 Example 5 Comparative example 1
Particle size 2231nm 767nm 536nm 238nm 366nm Non-emulsion
Time to stratification after standing 1d 7d 20d 360d 240d 0d
From the analyses of tables 1 and 2, comparison of examples 1,2 and 4 shows that grafted polyolefin polymers of different molecular weights can be used to prepare emulsions in a mixture of stearic acid and potassium hydroxide. The comparison of examples 1 and 2 shows that the particle size of the prepared polyolefin polymer aqueous emulsion is increased along with the increase of the weight average molecular weight of the grafted polyolefin polymer by using the same amount of acid-base mixture (inorganic base and organic base); this also indicates that the acid-base mixture in example 2 is used in an insufficient amount for the grafted polyolefin-based polymer having a high weight average molecular weight. Comparison of examples 1 and 3 shows that emulsions with better stability can be prepared with the addition of an emulsifier. Comparative example 1 shows that it is difficult to prepare an aqueous polyolefin polymer emulsion without using an acid-base mixture. The comparison of examples 4 and 5 shows that a stable emulsion can be prepared by using a small amount of acid-base mixture and a large amount of emulsifier. Compared with examples 2 and 4, the acid-base mixture is used independently and matched with amine substances to prepare stable emulsion; if the amount of the acid-base mixture is increased, emulsion with smaller particle size and more stability can be prepared.
A glass fiber sizing agent comprises 0.5-5 parts by mass of a coupling agent, 1-4 parts by mass of a lubricant, 1-10 parts by mass of an auxiliary film forming agent, 1-3 parts by mass of an antistatic agent, 100 parts by mass of 400 parts by mass of water and 30-50 parts by mass of the polyolefin polymer aqueous emulsion prepared by the method.
Preferably, the coupling agent is an amine-based silane coupling agent; the lubricant is preferably a cationic lubricant or a nonionic lubricant.
The polyolefin polymer aqueous emulsion with too large particle size has short storage period and unstable prepared impregnating compound, so the particle size of the polyolefin polymer aqueous emulsion for the glass fiber impregnating compound is preferably 150-400 nm.
The glass fiber sizing agents were prepared from the polyolefin polymer aqueous emulsions 4 and 5 obtained in examples 4 to 5, respectively, in the following proportions:
6.2 percent of polyolefin polymer aqueous emulsion 4, 0.9 percent of coupling agent, 1.4 percent of lubricant, 1.6 percent of auxiliary film-forming agent and 84.5 percent of water are mixed to obtain the glass fiber sizing agent 1.
6.2 percent of polyolefin polymer aqueous emulsion 5, 0.9 percent of coupling agent, 1.4 percent of lubricant, 1.6 percent of auxiliary film-forming agent and 84.5 percent of water are mixed to obtain the glass fiber impregnating compound 2.
Coating the glass fiber impregnating compound 1 and the glass fiber impregnating compound 2 on the surface of a glass fiber with the diameter of about 13 microns to obtain a glass fiber sample treated by the impregnating compound, and using the glass fiber sample for reinforcing polypropylene resin to respectively obtain a composite material sample strip 1 and a composite material sample strip 2.
Table 3 below shows the results of mechanical property measurements performed on the composite material sample strip 1 and the composite material sample strip 2. Therefore, the preparation method of the polyolefin polymer water-based emulsion is used for preparing the polyolefin polymer water-based emulsion, the glass fiber impregnating compound is prepared from the polyolefin polymer water-based emulsion, and the glass fiber reinforced polypropylene resin coated by the glass fiber impregnating compound has better mechanical property than the emulsion prepared by using a large amount of external emulsifier.
TABLE 3 mechanical Property test results of composite spline 1 and composite spline 2
Test items Composite material strip 1 Composite material strip 2
Glass fiber content (%) 30.9 31.2
Tensile Strength (MPa) 92.3 86.1
Flexural Strength (MPa) 147.3 141.0
Flexural modulus (GPa) 5.95 6.11
Notched impact (KJ/square meter) 14.2 12.7
Impact without gap (KJ/square meter) 50.1 47.4
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. An aqueous polyolefin polymer emulsion characterized by comprising 15 to 25 parts by mass of a grafted polyolefin polymer, 3 to 10 parts by mass of a fatty acid, 1 to 5 parts by mass of an inorganic base, 2 to 7 parts by mass of an organic base and 55 to 76 parts by mass of water; wherein the weight average molecular weight of the grafted polyolefin polymer is greater than 20000.
2. The aqueous polyolefin polymer emulsion of claim 1, wherein the grafted polyolefin polymer comprises one or more of a polyolefin blend of C2-C4, a polypropylene grafted acid, and a polypropylene grafted anhydride.
3. The aqueous polyolefin polymer emulsion of claim 2, wherein the polyolefin blend of C2-C4 comprises one or more of polyethylene, polyethylene-polypropylene copolymer, isotactic polypropylene, atactic polypropylene, polybutadiene, and polyisobutylene; or the polypropylene grafted acid comprises one or more of acrylic acid, methacrylic acid, methacrylate ester and acrylate ester; and/or the polypropylene grafted anhydride comprises one or more of maleic anhydride, acrylic anhydride, and methacrylic anhydride.
4. The aqueous polyolefin polymer emulsion of claim 1, wherein the fatty acid comprises a saturated fatty acid comprising one or more of behenic acid, stearic acid, lauric acid, myristic acid, caprylic acid succinate, capric acid, palmitic acid, arachidic acid.
5. The aqueous polyolefin polymer emulsion of claim 1, wherein the fatty acid comprises an unsaturated fatty acid comprising one or more of oleic acid, linoleic acid, linolenic acid, and arachidonic acid.
6. The aqueous polyolefin polymer emulsion of claim 1, wherein the inorganic base comprises one or more of sodium hydroxide, potassium hydroxide, and calcium hydroxide.
7. The aqueous polyolefin polymer emulsion of claim 1, wherein the organic base comprises one or more of ethanolamine, ethylenediamine, dimethylamine, isopropylamine, triethanolamine, tert-butylamine, octylamine, benzylamine, hexamethylenetetramine, o-aminophenol, o-toluidine, 8-hydroxyquinoline, and diphenylamine.
8. A method for preparing an aqueous polyolefin polymer emulsion as claimed in any of claims 1 to 7, comprising the steps of:
s1, mixing 15-25 parts by mass of a grafted polyolefin polymer, 3-10 parts by mass of fatty acid and 1-5 parts by mass of inorganic base, and fully melting and uniformly stirring at a temperature higher than the melting point of the grafted polyolefin polymer; to obtain a component 1;
s2, adding 2-7 parts by mass of organic base and 10-20 parts by mass of water mixture into the component 1 to obtain a component 2;
s3, stirring the component 2 at a temperature higher than the melting point of the grafted polyolefin polymer, adding 45-60 parts by mass of water, adjusting the solid content to be 30-40%, fully stirring, cooling to a temperature below the melting point, and thus obtaining the polyolefin polymer aqueous emulsion.
9. A glass fiber sizing agent is characterized by comprising 0.5-5 parts by mass of a coupling agent, 1-4 parts by mass of a lubricant, 1-10 parts by mass of an auxiliary film forming agent, 1-3 parts by mass of an antistatic agent, 100-400 parts by mass of water and 30-50 parts by mass of the polyolefin polymer aqueous emulsion prepared by the method of claim 8.
10. The glass fiber sizing agent according to claim 9, wherein the coupling agent comprises an amine-based silane coupling agent; and/or the lubricant comprises a cationic lubricant or a nonionic lubricant; and/or the particle size of the polyolefin polymer aqueous emulsion is 150nm-400 nm.
CN202210211715.6A 2022-03-04 2022-03-04 Polyolefin polymer aqueous emulsion and preparation method and application thereof Pending CN114591515A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4240944A (en) * 1979-02-12 1980-12-23 Ppg Industries, Inc. Emulsion composition and method for use in treating glass fibers
US5242969A (en) * 1989-04-19 1993-09-07 Vetrotex-Saint Gobain Aqueous polyolefin emulsions and method of forming same
US5389440A (en) * 1989-04-19 1995-02-14 Vetrotex Saint-Gobain Finish composition for coating and protecting a reinforcing substrate
US6166118A (en) * 1997-06-13 2000-12-26 Eastman Chemical Company Emulsification process for functionalized polyolefins and emulsions made therefrom
CN103044628A (en) * 2012-12-25 2013-04-17 中盈长江国际新能源投资有限公司 Preparation method of biomass-based polymer emulsion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4240944A (en) * 1979-02-12 1980-12-23 Ppg Industries, Inc. Emulsion composition and method for use in treating glass fibers
US5242969A (en) * 1989-04-19 1993-09-07 Vetrotex-Saint Gobain Aqueous polyolefin emulsions and method of forming same
US5389440A (en) * 1989-04-19 1995-02-14 Vetrotex Saint-Gobain Finish composition for coating and protecting a reinforcing substrate
US6166118A (en) * 1997-06-13 2000-12-26 Eastman Chemical Company Emulsification process for functionalized polyolefins and emulsions made therefrom
CN103044628A (en) * 2012-12-25 2013-04-17 中盈长江国际新能源投资有限公司 Preparation method of biomass-based polymer emulsion

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