Method for preparing photopolymerizable organosilicon polyurethane acrylate aqueous oligomer and composition thereof

Abstract

The invention discloses a method for preparing a photopolymerizable organosilicon polyurethane acrylate aqueous oligomer and a composition thereof. The method is based on the shortcomings of the current photopolymerizable organosilicon polyurethane acrylate aqueous oligomer, and the method comprises the following steps: synthesizing 2,2-bis(hydroxymethyl) butyl acrylate (HBA), and introducing thematerial into the oligomer molecule to make the polymer side chain is rich in unsaturated carbon-carbon double bonds; synthesizing one-terminated hydroxypolydimethylsiloxane (Si-OH), and introducing the substrate to the end of a main chain of the aqueous polyurethane acrylate oligomer so that the substrates facilitate enrichment on the surface of the material. Through the above molecular design, the problems of poor water resistance and low hardness of the aqueous photocurable material caused by the low double bond content and low crosslink density of the photocurable material are effectivelysolved, and the disadvantages that silicone chain is easily wrapped by the crosslinked network when is in the middle of the main chain so that the silicone is not enriched at the surface of the material, so that the surface hydrophobicity of the material can be effectively increased.

Description

technical field

[0001] The invention belongs to the technical field of macromolecular chemical materials, and in particular relates to a preparation method and a composition of a photopolymerizable silicone polyurethane acrylate water-based oligomer. Background technique

[0002] In recent years, with the strengthening of global environmental awareness, water-based UV curing materials have gradually entered everyone's field of vision. The water-based UV curing system uses water as a diluent to solve the environmental and health problems such as odor and toxicity caused by the addition of highly volatile low-molecular-weight oil-soluble monomers to adjust the viscosity and material properties of traditional UV curing materials. One of the main directions of material development. UV-curable polyurethane oligomer is a type of resin with the best comprehensiveness, easy preparation and easy adjustment of structural properties. It is widely used in various fields of photocuring....

Examples

Embodiment 1

[0051] Taking the synthesis of a photopolymerizable silicone urethane acrylate water-based oligomer as an example with the preferred raw materials, the synthesis principle is as follows:

[0052] The first step: react trimethylolpropane, 2,2-dimethoxypropane, p-toluenesulfonic acid and chloroform at 65°C for 16 hours, cool to room temperature, add anhydrous sodium carbonate and stir for 2 hours, Filtration, the filtrate was evaporated under reduced pressure to remove chloroform, and the product 1 was obtained; the molar ratio of trimethylolpropane to 2,2-dimethoxypropane was 1:1.1, and the amount of p-toluenesulfonic acid was trimethylolpropane 1% of the total mass of propane and 2,2-dimethoxypropane, and the molar ratio of anhydrous sodium carbonate to p-toluenesulfonic acid is 2:1. The reaction equation is as follows:

[0053]

[0054] The second step: react (meth)acryloyl chloride, triethylamine, product 1 and dichloromethane at 0°C for 2 hours, raise the temperature to...

Embodiment 2

[0076] A kind of preparation method of photopolymerizable organosilicon urethane acrylate aqueous oligomer, comprises the following steps:

[0077](1) Add 20.10g of trimethylolpropane (TMP) and 17.16g of 2,2-dimethoxypropane into a single-necked flask, add 30mL of chloroform solvent and 0.37g of p-toluenesulfonic acid, and heat at 65°C Stir under reflux, cool to room temperature after 16 hours, add 0.46 g of anhydrous sodium carbonate, stir at room temperature for 2 hours to end the reaction, filter, and remove chloroform from the filtrate by rotary evaporation under reduced pressure to obtain product 1;

[0078] (2) In a 250mL three-neck flask equipped with a spherical condenser, magnetic stirring, thermometer and dropping funnel, add 17.40g (0.1mol) of product 1, 11.11g (0.11mol) of triethylamine and 50mL of anhydrous dichloromethane , cooled to 0°C in an ice-water bath, slowly added dropwise 9.96g (0.11mol) of acryloyl chloride, stirred in an ice-water bath for 2 hours, the...

Embodiment 3-4

[0084] The steps of Example 2 were repeated, except that the amounts of PCDL, HBA, and IPDI were different, as shown in Table 1.

[0085] The add-on of table 1. PCDL used in embodiment 3-4, HBA, IPDI raw material

[0086] raw material

[0087] The aqueous oligomer obtained in embodiment 3-4 is named as PCDL-PEG-HBA respectively 12 -WSi 8 PUA, PCDL-PEG-HBA 15 -WSi 8 PUAs.

technical field

[0001] The invention belongs to the technical field of macromolecular chemical materials, and in particular relates to a preparation method and a composition of a photopolymerizable silicone polyurethane acrylate water-based oligomer. Background technique

[0002] In recent years, with the strengthening of global environmental awareness, water-based UV curing materials have gradually entered everyone's field of vision. The water-based UV curing system uses water as a diluent to solve the environmental and health problems such as odor and toxicity caused by the addition of highly volatile low-molecular-weight oil-soluble monomers to adjust the viscosity and material properties of traditional UV curing materials. One of the main directions of material development. UV-curable polyurethane oligomer is a type of resin with the best comprehensiveness, easy preparation and easy adjustment of structural properties. It is widely used in various fields of photocuring....

Examples

Embodiment 1

[0051] Taking the synthesis of a photopolymerizable silicone urethane acrylate water-based oligomer as an example with the preferred raw materials, the synthesis principle is as follows:

[0052] The first step: react trimethylolpropane, 2,2-dimethoxypropane, p-toluenesulfonic acid and chloroform at 65°C for 16 hours, cool to room temperature, add anhydrous sodium carbonate and stir for 2 hours, Filtration, the filtrate was evaporated under reduced pressure to remove chloroform, and the product 1 was obtained; the molar ratio of trimethylolpropane to 2,2-dimethoxypropane was 1:1.1, and the amount of p-toluenesulfonic acid was trimethylolpropane 1% of the total mass of propane and 2,2-dimethoxypropane, and the molar ratio of anhydrous sodium carbonate to p-toluenesulfonic acid is 2:1. The reaction equation is as follows:

[0053]

[0054] The second step: react (meth)acryloyl chloride, triethylamine, product 1 and dichloromethane at 0°C for 2 hours, raise the temperature to...

Embodiment 2

[0076] A kind of preparation method of photopolymerizable organosilicon urethane acrylate aqueous oligomer, comprises the following steps:

[0077](1) Add 20.10g of trimethylolpropane (TMP) and 17.16g of 2,2-dimethoxypropane into a single-necked flask, add 30mL of chloroform solvent and 0.37g of p-toluenesulfonic acid, and heat at 65°C Stir under reflux, cool to room temperature after 16 hours, add 0.46 g of anhydrous sodium carbonate, stir at room temperature for 2 hours to end the reaction, filter, and remove chloroform from the filtrate by rotary evaporation under reduced pressure to obtain product 1;

[0078] (2) In a 250mL three-neck flask equipped with a spherical condenser, magnetic stirring, thermometer and dropping funnel, add 17.40g (0.1mol) of product 1, 11.11g (0.11mol) of triethylamine and 50mL of anhydrous dichloromethane , cooled to 0°C in an ice-water bath, slowly added dropwise 9.96g (0.11mol) of acryloyl chloride, stirred in an ice-water bath for 2 hours, the...

Embodiment 3-4

[0084] The steps of Example 2 were repeated, except that the amounts of PCDL, HBA, and IPDI were different, as shown in Table 1.

[0085] The add-on of table 1. PCDL used in embodiment 3-4, HBA, IPDI raw material

[0086] raw material

[0087] The aqueous oligomer obtained in embodiment 3-4 is named as PCDL-PEG-HBA respectively 12 -WSi 8 PUA, PCDL-PEG-HBA 15 -WSi 8 PUAs.

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