UV rapid prototyping black polyurethane rubber material and preparation method thereof

Abstract

The invention discloses a UV rapid prototyping black polyurethane rubber material and a preparation method thereof, and belongs to the technical field of high polymer materials, the UV rapid prototyping black polyurethane rubber material comprises polyether amine modified acrylate, aliphatic polyurethane acrylate, an acrylate monomer, a first initiator, a second initiator, a polymerization inhibitor and black UV color paste; the acrylate monomer is one or a combination of two of cyclotrimethylolpropane methylal acrylate and isobornyl acrylate; the first initiator is one or a combination of more of ethyl 2, 4, 6-trimethylbenzoyl phenyl phosphonate, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl propane-1-ketone and 2, 2-dimethoxy-2-phenyl acetophenone, and the second initiator is one or a combination of more of ethyl 2, 4, 6-trimethylbenzoyl phenyl phosphonate, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl propane-1-ketone and 2, 2-dimethoxy-2-phenyl acetophenone. The problems that an existing ultraviolet light curing technology is insufficient in curing depth and long in curing time in a black system, and particularly curing is difficult in a deep layer material are solved. The advantages of deep curing and rapid curing are realized.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a UV rapid prototyping black polyurethane rubber material and a preparation method thereof. Background Art

[0002] UV light curing technology is a technology that quickly cures liquid materials through ultraviolet light irradiation. This technology has been widely used in many fields such as coatings, inks, adhesives, etc. due to its advantages such as fast curing speed, low energy consumption, and low environmental pollution. However, in the black system, due to the strong absorption of ultraviolet light by black materials, the light penetration ability is poor, and usually only curing can be achieved within a few millimeters of the surface. In the traditional UV curing process, especially for the black system, due to the strong absorption of ultraviolet light by black materials, the light penetration ability is poor. Under normal circumstances, ultraviolet light (especially ultraviolet light with a wavelength of less than 400nm) has weak penetration ability and can only penetrate a thickness of microns. Even 400nm ultraviolet light is difficult to penetrate a thickness of more than 1mm in the black system, which limits the curing depth of the black system.

[0003] Existing UV curing technology has the following limitations in black systems: (1) Insufficient curing depth: Due to the absorption of UV light by black materials, light curing can only be achieved within a few millimeters of the surface and cannot reach a deeper curing depth. (2) Long curing time: Traditional UV curing technology takes a long time to cure in black systems, making it difficult to achieve rapid curing. (3) Selection of initiators: Existing initiators are often difficult to fully cure within a few seconds in black systems, especially in deep materials.

[0004] Therefore, there is an urgent need for a UV rapid prototyping black polyurethane rubber material and a preparation method thereof to overcome the limitations of traditional UV curing in black systems and achieve a deeper curing depth and a faster curing speed. Summary of the invention

[0005] To this end, the present invention provides a UV rapid prototyping black polyurethane rubber material and a preparation method thereof, so as to solve the problems of insufficient curing depth and long curing time of the existing UV curing technology in black systems, especially the curing difficulty in deep materials.

[0006] In order to achieve the above object, the present invention provides the following technical solutions: According to a first aspect of the present invention, there is provided a UV rapid prototyping black polyurethane rubber material comprising the following components in parts by weight: 3-5 parts of polyetheramine modified acrylate, 40-50 parts of aliphatic polyurethane acrylate, 45-55 parts of acrylate monomer, 1-4 parts of first initiator, 0.3-0.8 parts of second initiator, 0.01-0.03 parts of inhibitor and 0.03-0.08 parts of black UV color paste.

[0007] Furthermore, the acrylate monomer is one or a combination of cyclotrimethylolpropane formal acrylate and isobornyl acrylate.

[0008] Furthermore, the first initiator is one or more combinations of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 2,2-dimethoxy-2-phenylacetophenone.

[0009] Furthermore, the second initiator is one or more combinations of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, benzoyl peroxide, and di-tert-butyl peroxide.

[0010] Furthermore, the polymerization inhibitor is one or more combinations of p-hydroxyanisole, hydroquinone, 2,6-di-tert-butyl-p-cresol, and 2,5-di-tert-butyl-hydroquinone.

[0011] According to a second aspect of the present invention, there is provided a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. The polyetheramine-modified acrylate, aliphatic polyurethane acrylate, acrylate monomer, first initiator, second initiator, inhibitor and black UV color paste weighed by weight are placed in a beaker of a normal temperature water bath, the temperature is maintained between 20-25°C, and a mechanical stirrer is used to stir until fully mixed; S2. Fill the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material at the location where the sealing strip is required, and use an LED ultraviolet lamp for light curing to obtain a black polyurethane rubber material.

[0012] Furthermore, the stirring speed of the mechanical stirrer in S1 is 500-1000 rpm, and the stirring time is 2-5 h.

[0013] Furthermore, in S2, the light curing time is 30-120s, the curing distance is 3-8cm, and the curing intensity is 30-60mW / cm².

[0014] The present invention has the following advantages: 1. Deep curing capability: Through a unique formula design, the present application utilizes the synergistic effect of the first initiator and the second initiator to achieve deep curing in the black system, with a curing depth of more than 10 mm, significantly exceeding the curing depth of traditional UV curing technology in the black system. Specifically, when the liquid material receives ultraviolet light, the first initiator rapidly decomposes to produce free radicals and releases heat, which activates the second initiator and triggers further polymerization reactions. The use of highly reactive polyetheramine-modified acrylates allows the entire curing process to be completed within seconds, and the curing depth can reach more than 10 mm. This dual initiation mechanism ensures that the material can be rapidly cured even at a deep level.

[0015] 2. Fast curing speed: This application achieves a curing process within seconds by optimizing the formula and curing process, greatly shortening the curing time of traditional UV curing technology in black systems. The polyetheramine-modified acrylate introduced in this application has high reactivity at a relatively low temperature. When used in combination with the second initiator and other ingredients in the formula, it can quickly initiate a polymerization reaction at a relatively low temperature, thereby achieving rapid curing of the material. DETAILED DESCRIPTION

[0016] The following is a description of the implementation of the present invention by specific embodiments. People familiar with the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] In this document, unless otherwise specified, all percentages, ratios or parts involved are by weight. "Parts by weight" refers to the basic unit of measurement of the weight ratio of multiple components, and 1 part can represent any unit weight, for example, 1 part can be represented as 1g, 1.5g, or 5g, etc.

[0018] The present invention provides a UV rapid prototyping black polyurethane rubber material, comprising the following components in parts by weight: 3-5 parts of polyetheramine modified acrylate, 40-50 parts of aliphatic polyurethane acrylate, 45-55 parts of acrylate monomer, 1-4 parts of first initiator, 0.3-0.8 parts of second initiator, 0.01-0.03 parts of inhibitor and 0.03-0.08 parts of black UV color paste.

[0019] Specifically, the acrylate monomer is one or a combination of cyclotrimethylolpropane formal acrylate and isobornyl acrylate.

[0020] Specifically, the first initiator is one or more combinations of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 2,2-dimethoxy-2-phenylacetophenone. Preferably, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester is selected in the present application.

[0021] Specifically, the second initiator is one or more combinations of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, benzoyl peroxide, and di-tert-butyl peroxide. Preferably, azobisisoheptanenitrile is selected in the present application.

[0022] Specifically, the polymerization inhibitor is one or more combinations of p-hydroxyanisole, hydroquinone, 2,6-di-tert-butyl-p-cresol, and 2,5-di-tert-butyl-hydroquinone. Preferably, p-hydroxyanisole is selected in the present application.

[0023] The present invention provides a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. The polyetheramine-modified acrylate, aliphatic polyurethane acrylate, acrylate monomer, first initiator, second initiator, inhibitor and black UV color paste weighed by weight are placed in a beaker of a normal temperature water bath, the temperature is maintained between 20-25°C, and a mechanical stirrer is used to stir until fully mixed; S2. Fill the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material at the location where the sealing strip is required, and use an LED ultraviolet lamp for light curing to obtain a black polyurethane rubber material.

[0024] The stirring speed of the mechanical stirrer in S1 is 500-1000 rpm, and the stirring time is 2-5 h.

[0025] Among them, the light curing time in S2 is 30-120s, the curing distance is 3-8cm, and the curing intensity is 30-60 mW / cm 2 .

[0026] Example 1 This embodiment provides a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. 5 g of polyetheramine-modified acrylate, 45 g of aliphatic polyurethane acrylate, 48 g of cyclotrimethylolpropane formal acrylate, 2 g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.5 g of azobisisoheptanenitrile, 0.02 g of p-hydroxyanisole and 0.05 g of black UV color paste were placed in a beaker at 25 ° C. in a water bath and stirred with a mechanical stirrer until fully mixed; S2. Pour the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material to the location where the sealing strip is required, and use an LED UV lamp to cure at a distance of 5 cm and 50 mW / cm 2 The black polyurethane rubber material used as the sealing strip can be obtained by light curing for 2 minutes with a curing strength of 1.54 W.

[0027] Example 2 This embodiment provides a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. 3 g of polyetheramine-modified acrylate, 50 g of aliphatic polyurethane acrylate, 45 g of isobornyl acrylate, 2 g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.5 g of azobisisoheptanenitrile, 0.02 g of p-hydroxyanisole and 0.05 g of black UV color paste were placed in a beaker at 25 ° C. in a water bath and stirred with a mechanical stirrer until fully mixed; S2. Pour the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material to the location where the sealing strip is required, and use an LED UV lamp to cure at a distance of 5 cm and 50 mW / cm 2 The black polyurethane rubber material used as the sealing strip can be obtained by light curing for 2 minutes with a curing strength of 1.54 W.

[0028] Example 3 This embodiment provides a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. 4 g of polyetheramine-modified acrylate, 48 g of aliphatic polyurethane acrylate, 45 g of cyclotrimethylolpropane formal acrylate, 2 g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.5 g of azobisisoheptanenitrile, 0.02 g of p-hydroxyanisole and 0.05 g of black UV color paste were placed in a beaker at 25 ° C. in a water bath and stirred with a mechanical stirrer until fully mixed; S2. Pour the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material at the location where the sealing strip is required, and use an LED UV lamp to cure at a distance of 5cm and 50mW / cm 2 The black polyurethane rubber material used as the sealing strip can be obtained by light curing for 2 minutes with a curing strength of 1.54 W.

[0029] Example 4

[0030] This embodiment provides a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. 5 g of polyetheramine-modified acrylate, 45 g of aliphatic polyurethane acrylate, 23 g of cyclotrimethylolpropane formal acrylate, 2 g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.5 g of azobisisoheptanenitrile, 0.02 g of p-hydroxyanisole and 0.05 g of black UV color paste were placed in a beaker at 25 ° C. in a water bath and stirred with a mechanical stirrer until fully mixed; S2. Pour the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material to the location where the sealing strip is required, and use an LED UV lamp to cure at a distance of 5 cm and 50 mW / cm 2 The black sealing strip can be obtained by light curing for 2 minutes with the curing strength of 100%.

[0031] Comparative Example 1 This embodiment provides a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. 50 g of aliphatic polyurethane acrylate, 48 g of cyclotrimethylolpropane formal acrylate, 2 g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.5 g of azobisisoheptanenitrile, 0.02 g of p-hydroxyanisole and 0.05 g of black UV color paste were placed in a beaker at 25 ° C. in a water bath and stirred with a mechanical stirrer until fully mixed; S2. Pour the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material to the location where the sealing strip is required, and use an LED UV lamp to cure at a distance of 5 cm and 50 mW / cm 2 The black sealing strip can be obtained by light curing for 2 minutes with the curing strength of 100%.

[0032] Comparative Example 2 This embodiment provides a method for preparing a UV rapid prototyping black polyurethane rubber material, comprising the following steps: S1. 5 g of polyetheramine-modified acrylate, 45 g of aliphatic polyurethane acrylate, 48 g of cyclotrimethylolpropane formal acrylate, 2 g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.02 g of p-hydroxyanisole and 0.05 g of black UV color paste were placed in a beaker at 25 ° C. in a water bath and stirred with a mechanical stirrer until fully mixed; S2. Pour the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material to the location where the sealing strip is required, and use an LED UV lamp to cure at a distance of 5 cm and 50 mW / cm 2 The black sealing strip can be obtained by light curing for 2 minutes with the curing strength of 100%.

[0033] Comparative Example 3: Commercially available die-cut rubber strip.

[0034] Test example: In order to evaluate the performance of the produced black polyurethane rubber material, we conducted the following tests on the black polyurethane rubber materials prepared in Examples 1-4 and Comparative Examples 1-3 in combination with practical applications: 1. Curing conditions: Use LED UV lamp with a wavelength of 405nm and a curing energy of 1000mJ / cm 2 .

[0035] 2. Test items: Shore hardness, surface curing condition, deep curing depth, elastic modulus.

[0036] The test results are shown in Table 1: Table 1: Performance test results of UV rapid prototyping black polyurethane rubber material

[0037] According to the test results of the embodiments and comparative examples, the following analysis and conclusions can be drawn: 1. Examples 1-4: The hardness ranges from D30 to A70, indicating that materials with different hardness can be obtained by adjusting different formulas. Among them, the hardness of Example 2 is D50, and the tensile strength is the highest (18MPa), showing good comprehensive performance. Comparative Examples 1-2: The hardnesses are A85 and A70, respectively, and the hardness is relatively high, but the surface curing and deep curing effects are not good, indicating that the lack of key ingredients in this formula (polyetheramine modified acrylate or second initiator) will lead to performance degradation. Comparative Example 3 (die-cut rubber strip): The hardness is A70, which is the same as that of Example 1, but the tensile strength is slightly lower (12MPa), indicating that Example 1 has better performance than commercially available die-cut rubber strips.

[0038] 2. Examples 1-4: The surfaces are smooth and non-sticky, indicating that the surface of the material has been completely cured and has good surface quality. Comparative Example 1-2: The surface is slightly sticky, indicating that the surface of the material is not completely cured, and the curing rate is reduced due to the lack of key components.

[0039] 3. Examples 1-4: The curing depths are all over 10 mm, indicating that the material can achieve good curing effect even in deep layers and is suitable for applications requiring deep curing. Comparative Examples 1-2: The curing depths are lower than 2 mm and 1.5 mm, respectively, indicating that the lack of polyetheramine-modified acrylate or the second initiator leads to a significant reduction in the curing depth.

[0040] 4. Example 1-4: The tensile strength is between 12-18 MPa, indicating that the material has good mechanical properties. Comparative Example 1-2: The tensile strength is lower (9 MPa and 8 MPa), indicating that the lack of key components not only affects the curing effect, but also reduces the overall performance of the material.

[0041] In summary, the hardness (A70) of Example 1 is the same as that of the die-cut rubber strip, but the tensile strength is higher, indicating that the formula and method of the present invention can be used to prepare a material with better performance than the commercial die-cut rubber strip. The hardness (D50) and tensile strength (18 MPa) of Example 2 are both excellent, and the overall performance is the best. Comparative Example 1 lacks polyetheramine-modified acrylate, resulting in a lower curing rate, poor curing depth and surface curing effect. This shows that the polyetheramine-modified acrylate in this formula plays an important role in improving the curing rate and deep curing. Comparative Example 2 lacks a second initiator, resulting in a significant reduction in the curing depth. This shows that the second initiator promotes deep curing through a thermal initiation mechanism in the black system and increases the curing depth. All examples showed good surface and deep curing effects when cured using an LED ultraviolet lamp with a wavelength of 405nm and a curing energy of 1000mJ / cm². By comparing and analyzing the data of the embodiments and comparative examples, it can be concluded that the formula and method of the present invention have obvious advantages in preparing UV rapid prototyping black polyurethane rubber materials, especially in improving the deep curing depth and surface curing quality. By reasonably selecting and proportioning the components, the performance of the material can be further optimized to meet the needs of different application scenarios.

[0042] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A UV rapid prototyping black polyurethane rubber material, characterized in that: It comprises the following components in parts by weight: 3-5 parts of polyetheramine modified acrylate, 40-50 parts of aliphatic polyurethane acrylate, 45-55 parts of acrylate monomer, 1-4 parts of first initiator, 0.3-0.8 parts of second initiator, 0.01-0.03 parts of inhibitor and 0.03-0.08 parts of black UV color paste.

2. The UV rapid prototyping black polyurethane rubber material according to claim 1, characterized in that: The acrylic acid ester monomer is one or a combination of cyclotrimethylolpropane formal acrylate and isobornyl acrylate.

3. The UV rapid prototyping black polyurethane rubber material according to claim 1, characterized in that: The first initiator is one or more combinations of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 2,2-dimethoxy-2-phenylacetophenone.

4. The UV rapid prototyping black polyurethane rubber material according to claim 1, characterized in that: The second initiator is one or more combinations of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, benzoyl peroxide, and di-tert-butyl peroxide.

5. The UV rapid prototyping black polyurethane rubber material according to claim 1, characterized in that: The polymerization inhibitor is one or more combinations of p-hydroxyanisole, hydroquinone, 2,6-di-tert-butyl-p-cresol, and 2,5-di-tert-butyl-hydroquinone.

6. A method for preparing a UV rapid prototyping black polyurethane rubber material, characterized in that: The following steps are involved: S1. The polyetheramine-modified acrylate, aliphatic polyurethane acrylate, acrylate monomer, first initiator, second initiator, inhibitor and black UV color paste weighed by weight are placed in a beaker of a normal temperature water bath, the temperature is maintained between 20-25°C, and a mechanical stirrer is used to stir until fully mixed; S2. Fill the mixture obtained in S1 into a black rubber cylinder, use a dispensing device to apply liquid polyurethane material at the location where the sealing strip is required, and use an LED ultraviolet lamp for light curing to obtain a black polyurethane rubber material.

7. The method for preparing the UV rapid prototyping black polyurethane rubber material according to claim 6, characterized in that: The stirring speed of the mechanical stirrer in S1 is 500-1000 rpm, and the stirring time is 2-5 h.

8. The method for preparing the UV rapid prototyping black polyurethane rubber material according to claim 6, characterized in that: In the S2, the light curing time is 30-120s, the curing distance is 3-8cm, and the curing intensity is 30-60 mW / cm².

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