Organic silicon modified polyolefin water-based resin and application thereof

Abstract

The invention relates to the field of resin, in particular to organic silicon modified polyolefin water-based resin which is prepared from the following raw materials in percentage by weight: 1-20% of chlorinated polypropylene, 10-60% of high-boiling-point alcohol ether, 0.1-5% of an azo compound, 1-10% of an organic silicon monomer and 20-70% of a polymeric monomer, and the boiling point of the high-boiling-point alcohol ether is 120-260 DEG C. The organic silicon modified polyolefin water-based resin obtained by the invention has good water solubility, does not contain the compound or other heavy metal substances in formula components, is non-toxic to human health, and has excellent performances in the aspects of water resistance, weather resistance, wear resistance, stain resistance, scrubbing resistance, adhesive force and the like after being cured.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of resin, in particular to a kind of organic silicon modified polyolefin water-based resin and its application. BACKGROUND

[0002] Polyolefin is a kind of thermoplastic resin modified by chlorination of polypropylene, which can be divided into low-chlorinated chlorinated polypropylene and high-chlorinated chlorinated polypropylene according to different chlorination reactions. The low-chlorinated chlorinated polypropylene has low polarity and poor water compatibility, and insufficient water resistance, which affects the adhesion in the field of coating and paint film, so it needs to be further modified.

[0003] The existing technology mainly improves the compatibility with water and adhesion performance by introducing polar groups or copolymerization modification to modify chlorinated polypropylene, but there are generally problems such as poor weather resistance and low mechanical strength. The present application copolymerizes organic silicon segment and acrylic monomer, which not only significantly improves the water resistance and adhesion of the resin, but also enhances the wear resistance and flexibility of the paint film, which is suitable for surface coating of automotive interior parts, and effectively improves the stability and durability of the coating in complex environment. SUMMARY

[0004] A kind of organic silicon modified polyolefin water-based resin, characterized in that, by weight percentage, the preparation raw materials include: chlorinated polypropylene 1-20%, high-boiling alcohol ether 10-60%, azo compound 0.1-5%, organic silicon monomer 1-10%, polymerization monomer 20-70%, and the boiling point of the high-boiling alcohol ether is 120-260℃.

[0005] Further, by weight percentage, the preparation raw materials include: chlorinated polypropylene 2-9%, high-boiling alcohol ether 15-40%, azo compound 0.4-1.2%, polymerization monomer 35-60%, and the boiling point of the high-boiling alcohol ether is 120-260℃.

[0006] Further, characterized in that, the high-boiling alcohol ether includes at least one of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether.

[0007] Further, the azo compound includes at least one of azobis isopropyl cyanide, azobis isobutyl cyanide, azobis isobutyl cyanide dimethyl ester, azobis isobutyl cyanide imidazoline hydrochloride, azobis isobutyl cyanide imidazoline hydrochloride and azobis isobutyl cyanamide.

[0008] Further, the organosilicon monomer includes at least one of methylvinyl dichlorosilane, vinyltrichlorosilane, divinyl dichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethyldivinyl disiloxane, gamma-(methacryloyloxy)propyltrimethoxysilane, allyl glycidyl ether polysiloxane.

[0009] Further, the polymerization monomer includes at least one of styrene, lauryl methacrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethoxyethyl methacrylate, ethylene glycol dimethacrylate.

[0010] Further, the polymerization monomer further includes a fluorine-containing acrylic monomer.

[0011] Further, the polymerization monomer is styrene, lauryl methacrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethoxyethyl methacrylate, a fluorine-containing acrylic monomer, ethylene glycol dimethacrylate.

[0012] Further, the polymerization monomer is styrene 2-6%, lauryl methacrylate 4-9%, methacrylic acid 1-2%, methyl methacrylate 25-35%, butyl methacrylate 10-20%, isobutyl methacrylate 10-20%, ethoxyethyl methacrylate 2-6%, a fluorine-containing acrylic monomer 4-10%, ethylene glycol dimethacrylate 6-10% by weight percentage.

[0013] The present application also provides an application of the organosilicon-modified polyolefin aqueous resin in the field of automotive interior decoration.

[0014] Automotive interior parts commonly use various plastic substrates, requiring extremely high performance in terms of water and acid / alkali resistance for the surface coating. The need for water-based coatings has long been a pain point in the industry. Existing technologies modify water-based resins by introducing polar groups through chlorination of polypropylene or by copolymerization to improve their compatibility with water and adhesion to plastics, but these methods generally suffer from poor weather resistance and low mechanical strength. This invention introduces hydrophobic organosilicon segments and copolymerizes them with acrylic monomers. Without compromising weather resistance, this forms hydrophobic, flexible long chains, significantly improving the resin's water and acid / alkali resistance, and also enhancing the abrasion resistance and flexibility of the paint film. The Si-O-Si bonds in the organosilicon segments and the organic groups (such as methyl groups) in the side chains give them extremely low surface energy, endowing the copolymer with excellent hydrophobicity and water penetration resistance. The long bond length and large bond angle of the Si-O bonds result in highly flexible molecular chains, giving the copolymer excellent low-temperature elasticity and flexibility. The high chemical bond energy of the organosilicon segments makes them resistant to UV degradation and provides good thermal stability, which are inherent advantages. The improved water-based resin is suitable for surface coating of automotive interior parts, effectively enhancing the stability and durability of the coating in complex environments.

[0015] The organosilicon-modified polyolefin waterborne resin obtained by this invention has good water solubility, and the formulation contains no organosilicon compounds or other heavy metal substances. It is non-toxic to human health. After curing, it has excellent performance in terms of water resistance, weather resistance, wear resistance, stain resistance, scrubbing resistance, and adhesion, and has broad application prospects. Detailed Implementation

[0016] To address the aforementioned technical problems, the first aspect of this invention provides an organosilicon-modified polyolefin aqueous resin, wherein the raw materials for preparation, by weight percentage, include: 1-20% chlorinated polypropylene, 10-60% high-boiling-point alcohol ether, 0.1-5% azo compound, 1-10% organosilicon monomer, and 20-70% polymeric monomer, wherein the high-boiling-point alcohol ether has a boiling point of 120-260°C.

[0017] Preferably, the raw materials for preparation, by weight percentage, include: 2-9% chlorinated polypropylene, 15-40% high-boiling-point alcohol ether, 0.4-1.2% azo compound, 2-5% organosilicon monomer, 35-60% polymeric monomer, wherein the high-boiling-point alcohol ether has a boiling point of 120-260℃.

[0018] Preferably, the chlorine content of the chlorinated polypropylene is 20-41 wt%.

[0019] Preferably, the chlorine content of the chlorinated polypropylene is 24-30 wt%.

[0020] Preferably, the viscosity (25°C) of the chlorinated polypropylene is 20-500 mPa·s.

[0021] Preferably, the chlorinated polypropylene is of type 1122S, with a chlorine content of 24.5 wt% and a viscosity (25°C) of 80 mPa·s.

[0022] In a preferred embodiment, the high-boiling-point alcohol ether includes at least one of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.

[0023] Preferably, the high-boiling-point alcohol ether is ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, or diethylene glycol butyl ether.

[0024] Preferably, the mass ratio of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, and diethylene glycol butyl ether is (1-5):(0.6-3.5):(0.5-2.8):1.

[0025] Preferably, the mass ratio of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, and diethylene glycol butyl ether is (1-3):(1.2-2.6):(0.9-1.7):1.

[0026] In a preferred embodiment, the azo compound includes at least one of azobisisoheptanenitrile, azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyramidin hydrochloride, and azobisisobutyronitrile cyanoformamide.

[0027] Preferably, the azo compound is azobisisobutyronitrile.

[0028] In a preferred embodiment, the polymeric monomer includes at least one of styrene, lauryl methacrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethoxyethyl methacrylate, and ethylene glycol dimethacrylate.

[0029] In a preferred embodiment, the organosilicon monomer includes at least one of methyl vinyl dichlorosilane, vinyl trichlorosilane, divinyl dichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, tetramethyl divinyl disiloxane, γ-(methacryloyloxy)propyl trimethoxysilane, and allyl glycidyl ether polysiloxane.

[0030] Preferably, the organosilicon monomer is methylvinyldichlorosilane.

[0031] Preferably, the polymerizing monomer is styrene, lauryl methacrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethoxyethyl methacrylate, fluorinated acrylic monomer, or ethylene glycol dimethacrylate.

[0032] Preferably, by weight percentage, the polymeric monomers are 2-6% styrene, 4-9% lauryl methacrylate, 1%-2% methacrylic acid, 25-35% methyl methacrylate, 10-20% butyl methacrylate, 10-20% isobutyl methacrylate, 2-6% ethoxyethyl methacrylate, 4-10% fluorinated acrylic monomers, and 6-10% ethylene glycol dimethacrylate.

[0033] Preferably, by weight percentage, the polymeric monomers are 5% styrene, 7% lauryl methacrylate, 2% methacrylic acid, 32% methyl methacrylate, 19% butyl methacrylate, 16% isobutyl methacrylate, 5% ethoxyethyl methacrylate, 6% fluorinated acrylic monomer, and 8% ethylene glycol dimethacrylate.

[0034] Preferably, the fluorinated acrylic monomer is dodecafluoroheptyl methacrylate.

[0035] A second aspect of the present invention provides an application of an organosilicon-modified polyolefin waterborne resin in the automotive interior materials field. Preferably, by weight percentage, the polymeric monomers are 2-6% styrene, 4-9% lauryl methacrylate, 1%-2% methacrylic acid, 25-35% methyl methacrylate, 10-20% butyl methacrylate, 10-20% isobutyl methacrylate, 2-6% ethoxyethyl methacrylate, 4-10% fluorinated acrylic monomers, and 6-10% ethylene glycol dimethacrylate.

[0036] Preferably, by weight percentage, the polymeric monomers are 5% styrene, 7% lauryl methacrylate, 2% methacrylic acid, 32% methyl methacrylate, 19% butyl methacrylate, 16% isobutyl methacrylate, 5% ethoxyethyl methacrylate, 6% fluorinated acrylic monomer, and 8% ethylene glycol dimethacrylate.

[0037] Preferably, the fluorinated acrylic monomer is dodecafluoroheptyl methacrylate.

[0038] A second aspect of the present invention provides an application of an organosilicon-modified polyolefin waterborne resin in the field of automotive interiors.

[0039] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0040] Chlorinated polypropylene-1122S was purchased from Shanghai WaiDian International Trading Co., Ltd. Azobisisobutyronitrile (AIORT) CAS: 78-67-1 Methylvinyl dichlorosilane CAS: 102-32-9 Ethylene glycol dimethacrylate CAS: 97-90-5 The dispersant BYK-2020 was purchased from Guangzhou Siteyuan Chemical Co., Ltd. Leveling agent HY-5057 was purchased from Beijing Maier Chemical Technology Co., Ltd. In addition, unless otherwise stated, all raw materials used are commercially available.

[0041] Example 1 The first aspect of this embodiment provides an organosilicon-modified polyolefin waterborne resin, the raw materials of which, by weight percentage, include: 6% chlorinated polypropylene-1122S (chlorine content of 24.5 wt%, viscosity (25°C) of 80 mPa·s), 35% high-boiling-point alcohol ether, 0.8% azobisisobutyronitrile, 5% methylvinyl dichlorosilane, and 53.2% polymeric monomers.

[0042] The high-boiling-point alcohol ether is a mixture of ethylene glycol butyl ether (boiling point 171℃), propylene glycol methyl ether (boiling point 120℃), propylene glycol butyl ether (boiling point 170.1℃), and diethylene glycol butyl ether (boiling point 231℃) in a mass ratio of 2:1.8:1.3:1.

[0043] By weight percentage, the polymeric monomers are 5% styrene, 7% lauryl methacrylate, 2% methacrylate, 32% methyl methacrylate, 19% butyl methacrylate, 16% isobutyl methacrylate, 5% ethoxyethyl methacrylate, 6% dodecafluoroheptyl methacrylate, and 8% ethylene glycol dimethacrylate.

[0044] The second aspect of this embodiment provides an application of organosilicon-modified polyolefin waterborne resin in the field of automotive interiors.

[0045] The first aspect of this comparative example provides an organosilicon-modified polyolefin waterborne resin. The specific implementation method is the same as that in Example 1, except that, by weight percentage, the polymeric monomers are 6% styrene, 9% butyl acrylate, 2% acrylic acid, 30% methyl methacrylate, 11% butyl methacrylate, 20% isobutyl methacrylate, 2% isooctyl methacrylate, 10% hexafluorobutyl acrylate, and 10% hydroxyethyl methacrylate.

[0046] The second aspect of this comparative example provides an application of an organosilicon-modified polyolefin waterborne resin in the field of automotive interiors.

[0047] The first aspect of this comparative example provides an organosilicon-modified polyolefin aqueous resin, with the specific implementation method being the same as in Example 1, except that glycerol monomethyl ether (boiling point 106.2℃) is used instead of high-boiling-point alcohol ether.

[0048] The second aspect of this comparative example provides an application of an organosilicon-modified polyolefin waterborne resin in the field of automotive interiors.

[0049] Comparative Example 3 The first aspect of this comparative example provides an organosilicon-modified polyolefin waterborne resin, with the specific implementation method being the same as in Example 1, except that the high-boiling-point alcohol ether is a mixture of ethylene glycol butyl ether (boiling point 171°C), propylene glycol methyl ether (boiling point 120°C), propylene glycol butyl ether (boiling point 170.1°C), and diethylene glycol butyl ether (boiling point 231°C) in a mass ratio of 2:5:5:1.

[0050] The second aspect of this comparative example provides an application of an organosilicon-modified polyolefin waterborne resin in the field of automotive interiors.

[0051] Comparative Example 4 The first aspect of this comparative example provides an organosilicon-modified polyolefin waterborne resin, with the specific implementation method being the same as in Example 1, except that vinyltrichlorosilane is used instead of methylvinyldichlorosilane.

[0052] The second aspect of this comparative example provides an application of an organosilicon-modified polyolefin waterborne resin in the field of automotive interiors.

[0053] After uniformly mixing the monomers in the above examples and comparative examples, chlorinated polypropylene-1122S and high-boiling-point alcohol ether were added and heated together. Azobisisobutyronitrile was added dropwise, followed by emulsification with an equal mass of deionized water to the monomers. The mixture was kept at 25°C for 1 hour and then discharged.

[0054] By weight, 40 parts of the waterborne resin from the above examples and comparative examples were mixed with 25 parts of titanium dioxide, 1 part of carbon black, 0.5 parts of dispersant BYK-2020, 7.5 parts of methylcyclohexane, 3 parts of butanone, and 0.2 parts of leveling agent HY-5057 to prepare a coating.

[0055] The above coating was applied to automotive interior parts (polypropylene plastic) with a coating thickness of approximately 25 μm, and then baked in an oven at 80°C for 30 minutes. The performance results are as follows: Adhesion testing standard reference: GB / T9286-88, rating standards are as follows: Level 0: The cut edges are completely smooth, with no chips falling off; Level 1: A small amount of thin film separation occurs at the intersection of the cuts, but the affected area in the gridded area is no more than 5%; Level 2: The coating at the intersection of the cuts is significantly greater than 5% and less than 15%; Level 3: The coating peels off in large fragments along the cut edge, or falls on different parts of the grid, with partial or complete peeling exceeding 5%, but the affected area is not significantly greater than 35%. Level 4: Coating peels off along the cut edge, with large fragments falling off, or some squares partially or completely peeling off, significantly more than 35%, but the impact is significantly less than 65%. Level 5: Severe flaking greater than Level 4.

[0056] Pencil hardness testing standard reference: GB / T6739-1996 The weather resistance test method is as follows: irradiate under a xenon lamp for 2000 hours and observe the surface changes; the color difference test standard refers to GB / T1865-2009. Abrasion resistance testing standard reference: GB / T23988-2009; The acid resistance test method is as follows: immerse in 6% sulfuric acid at 40 degrees Celsius for 3 hours, observe the surface changes, and test the adhesion.

[0057] The alkali resistance test method is as follows: immerse in 5% sodium carbonate at 40 degrees Celsius for 24 hours, observe the surface changes, and test the adhesion.

[0058] The method for testing boiling water resistance is as follows: immerse the sample in boiling water for 4 hours, observe the surface changes, and test the adhesion.

[0059]

[0060] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or equivalent modifications to the above-disclosed technical content. However, any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A silicone-modified polyolefin waterborne resin, characterized in that, The raw materials for preparation, by weight percentage, include: 1-20% chlorinated polypropylene, 10-60% high-boiling-point alcohol ether, 0.1-5% azo compound, 1-10% organosilicon monomer, and 20-70% polymeric monomer, wherein the high-boiling-point alcohol ether has a boiling point of 120-260℃.

2. The organosilicon-modified polyolefin waterborne resin according to claim 1, characterized in that, The raw materials for preparation, by weight percentage, include: 2-9% chlorinated polypropylene, 15-40% high-boiling-point alcohol ether, 0.4-1.2% azo compound, and 35-60% polymeric monomer, wherein the high-boiling-point alcohol ether has a boiling point of 120-260℃.

3. The organosilicon-modified polyolefin waterborne resin according to claim 1 or 2, characterized in that, The high-boiling-point alcohol ethers include at least one of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.

4. The organosilicon-modified polyolefin waterborne resin according to claim 1 or 2, characterized in that, The azo compound includes at least one of azobisisoheptanenitrile, azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azobisisobutyrimidoxoline hydrochloride, and azobisisobutyroxycyanoformamide.

5. The organosilicon-modified polyolefin waterborne resin according to claim 1 or 2, characterized in that, The organosilicon monomers include at least one of methylvinyl dichlorosilane, vinyl trichlorosilane, divinyl dichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, tetramethyl divinyl disiloxane, γ-(methacryloyloxy)propyl trimethoxysilane, and allyl glycidyl ether polysiloxane.

6. The organosilicon-modified polyolefin waterborne resin according to claim 1 or 2, characterized in that, The polymer monomers include at least one of styrene, lauryl methacrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethoxyethyl methacrylate, and ethylene glycol dimethacrylate.

7. The organosilicon-modified polyolefin waterborne resin according to claim 6, characterized in that, The polymer monomers also include fluorinated acrylic acid monomers.

8. The organosilicon-modified polyolefin waterborne resin according to claim 7, characterized in that, The polymer monomers are styrene, lauryl methacrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethoxyethyl methacrylate, fluorinated acrylic monomers, and ethylene glycol dimethacrylate.

9. The organosilicon-modified polyolefin waterborne resin according to claim 8, characterized in that, By weight percentage, the polymeric monomers are 2-6% styrene, 4-9% lauryl methacrylate, 1%-2% methacrylic acid, 25-35% methyl methacrylate, 10-20% butyl methacrylate, 10-20% isobutyl methacrylate, 2-6% ethoxyethyl methacrylate, 4-10% fluorinated acrylic monomers, and 6-10% ethylene glycol dimethacrylate.

10. An organosilicon-modified polyolefin waterborne resin according to any one of claims 7-9, applied in the field of automotive interiors.

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