Fluororubber and brominated butyl rubber co-vulcanization system and preparation method thereof
By using triazine vulcanizing agents and HVA-2 to form co-crosslinking bonds at the interface between fluororubber and brominated butyl rubber, the interfacial delamination problem was solved, improving the overall performance and reliability of the protective material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-25
- Publication Date
- 2026-03-31
AI Technical Summary
The lack of effective cross-linking at the interface between fluororubber and brominated butyl rubber leads to delamination, affecting the overall protective performance of the material.
A co-vulcanization system was prepared by using triazine vulcanizing agent (TCY) and HVA-2 as co-crosslinking agents to form co-crosslinking bonds at the interface between fluororubber and brominated butyl rubber, thereby adjusting the vulcanization rate of the two rubbers.
Effective cross-linking of fluororubber and brominated butyl rubber at the interface was achieved, eliminating the delamination problem, improving the overall protective performance, abrasion resistance and flexural resistance of the material, and enhancing the safety and reliability of the protective clothing.
Smart Images
Figure CN121760210A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of protective material preparation technology, specifically to a co-vulcanization system of fluororubber and brominated butyl rubber and its preparation method. Background Technology
[0002] Currently, many domestic and international protective clothing manufacturers are using multi-layer polymer films or multi-layer rubber composites to improve protective capabilities, based on the different material properties. This cross-protection with different materials achieves protection against numerous chemicals and toxic agents. However, polymer film materials tend to stiffen at low temperatures, resulting in poor comfort for wearers. Therefore, high-end protective clothing still primarily uses rubber materials, especially (halogenated) butyl rubber and fluororubber.
[0003] Fluororubber possesses high chemical stability and offers excellent protection against most organic solvents, inorganic solvents, and pharmaceuticals. (Halogenated) butyl rubber not only retains the excellent airtightness, aging resistance, and heat resistance of ordinary butyl rubber but also enhances its chemical reactivity through the introduction of halogen atoms (such as bromine). Both materials exhibit good airtightness, high and low temperature resistance, and aging resistance. However, brominated butyl rubber is a non-polar material, thus offering poor protection against benzene-based chemicals; fluororubber, being a polar material, offers poor protection against small molecules such as acetone. Theoretically, a composite of these two materials could provide effective protection against almost all common chemicals.
[0004] In the existing technology, most personal protective equipment companies at home and abroad have carried out the design of fluororubber and (halogenated) butyl rubber composite materials. For example, the French KI protective clothing is made of fluororubber and butyl rubber; Shanxi Xinhua Chemical Defense Equipment Research Institute Co., Ltd. also conducts research on fluororubber and chlorinated butyl rubber composite materials.
[0005] However, due to the large difference in polarity and mismatch in vulcanization speed between the two materials, if the two materials are directly composited by coating or calendering, delamination is very likely to occur due to the lack of effective cross-linking between the interfaces. To solve this problem, the common practice is to coat the two materials separately on both sides of the base fabric. The problem that follows is that the two materials cannot be effectively bonded at the seam during molding, making it a weak point and the protective performance does not meet the overall performance requirements of the fabric.
[0006] Based on this, this application proposes a co-vulcanization system of fluororubber and brominated butyl rubber and its preparation method. Summary of the Invention
[0007] To address the problem that current protective materials often lack effective cross-linking at the interface between fluororubber and (halogenated) butyl rubber, which easily leads to delamination and prevents effective bonding between the two materials, resulting in overall protective performance failing to meet fabric performance requirements, this invention provides a co-vulcanization system of fluororubber and brominated butyl rubber and its preparation method.
[0008] This invention is achieved using the following techniques: This invention provides a co-vulcanization system of fluororubber and brominated butyl rubber, comprising a triazine vulcanizing agent (TCY) and HVA-2; The triazine vulcanizing agent is used as a co-crosslinking agent to form co-crosslinking bonds at the interface between fluororubber and brominated butyl rubber; The HVA-2 is used to adjust and match the vulcanization rate of the fluororubber and the brominated butyl rubber.
[0009] Further, it includes a fluororubber layer and / or a brominated butyl rubber layer, wherein, based on 100 parts by weight of fluororubber, the amount of the triazine vulcanizing agent is 0.5 to 3 parts, and the amount of HVA-2 is 0.5 to 1.5 parts; In the brominated butyl rubber layer, based on 100 parts by weight of brominated butyl rubber, the amount of the triazine vulcanizing agent is 0.5 to 3 parts, and the amount of HVA-2 is 0.5 to 1.5 parts.
[0010] This invention provides a composite material comprising a base fabric layer, a fluororubber layer, and a brominated butyl rubber layer. The base fabric layer is made of polyester-cotton fabric, aramid fabric, nylon fabric, or polyester fabric. The fluororubber layer and the brominated butyl rubber layer are co-crosslinked through a vulcanization system to achieve interfacial co-crosslinking. The components of the fluororubber layer, by weight, include: Fluororubber: 100 parts; Bisphenol AF: 1.5–3 parts; Accelerator BPP: 0.1-1 part; Magnesium oxide: 0.5–3 parts; Calcium hydroxide: 2-6 parts; Calcium oxide: 0.5–3 parts; Triazine vulcanizing agent: 0.5–3 parts; HVA-2: 0.5–1.5 parts; The components of the brominated butyl rubber layer, by weight, include: Brominated butyl rubber: 100 parts; BIBP: 0.5–1.5 parts; Triazine vulcanizing agent: 0.5–3 parts; HVA-2: 0.5–1.5 parts; Zinc oxide: 0.5–1.5 parts; Stearic acid: 0.5–1.5 parts; Magnesium oxide: 0.5 to 1 part.
[0011] The components of the fluororubber layer (2) and the brominated butyl rubber layer (1) also include 0 to 5 parts of lightfast yellow, excluding 0 parts.
[0012] As an alternative, brominated butyl rubber can be replaced with chlorinated butyl rubber, and BIBP can be replaced with bis-2,5-diisopropylbenzene peroxide.
[0013] This invention provides a method for preparing a composite material, comprising the following steps: a) Mix the fluororubber layer component and the brominated butyl rubber layer component evenly to prepare brominated butyl rubber compound and fluororubber compound for later use; dissolve the brominated butyl rubber compound and the fluororubber compound in solvents to obtain fluororubber paste and brominated butyl rubber paste respectively; the weight ratio of brominated butyl rubber compound to solvent gasoline is 1:2; the weight ratio of ethyl acetate solvent to fluororubber compound is 1:4.
[0014] b. A fluororubber layer (2) and a brominated butyl rubber layer (1) are sequentially coated on one side of the base fabric layer (3) to form a laminate; the other side is coated with a brominated butyl rubber layer (1).
[0015] Specifically, the following steps are included: A 1.5-meter-wide polyester-cotton fabric was selected as the base fabric layer (3). Fluororubber adhesive was first coated on one side of the base fabric layer (3), with an adhesive application rate of 120g / m. 2 Then, brominated butyl rubber adhesive is coated onto the fluororubber layer, with an application rate of 50 g / m². 2 After applying a release agent (such as talc or corn starch), flip the fabric over. Then, coat the other side of the base fabric layer with brominated butyl rubber adhesive at a rate of 100 g / m². 2 .
[0016] c. After the solvent evaporates, vulcanization is performed under the following conditions: 145℃ × 1.5h and pressure 0.35~0.45MPa, to obtain the composite material.
[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a co-vulcanization system of fluororubber and brominated butyl rubber and its preparation method. By forming strong co-crosslinking bonds at the interface of the two rubbers, the interfacial delamination problem caused by polarity differences and mismatched vulcanization rates is solved. The brominated butyl rubber and fluororubber are vulcanized simultaneously, making the vulcanization processes of the two materials similar. Moreover, the effective crosslinking of the interface between fluororubber and brominated butyl rubber is achieved by using a triazine vulcanizing agent (TCY) + HVA-2, which solves the delamination problem between the two materials.
[0018] The prepared co-vulcanized rubber sheet material has excellent overall protective performance, with good protective properties, abrasion resistance, and flexural resistance. The protective performance of the fabric and its seams is more consistent. Even after doubling the abrasion resistance and flexural resistance tests, no delamination or peeling was observed, indicating that the interfacial bonding strength between brominated butyl rubber and fluororubber is good. This eliminates the weak points in protection caused by poor seam adhesion and improves the overall safety and reliability of the protective clothing. Attached Figure Description
[0019] Figure 1 This diagram illustrates the structure of a composite material according to the present invention. The diagram only shows the layer structure and does not show the layer thickness.
[0020] In the diagram: 1-bromobutyl rubber layer, 2-fluororubber layer, 3-base fabric layer. Detailed Implementation
[0021] The specific embodiments of the present invention will be described in detail below. Example 1
[0022] A method for preparing a composite material, such as Figure 1 As shown, the steps are as follows: a. On the open mill, control the roller temperature and mix brominated butyl rubber and fluororubber evenly to prepare brominated butyl rubber compound and fluororubber compound for later use. The components of the fluororubber layer, by weight, include: Fluororubber: 100 parts; Bisphenol AF: 1.5 parts; Accelerator BPP: 0.5 parts; Magnesium oxide: 1 part; Calcium hydroxide: 6 parts; Calcium oxide: 1 part; Triazine-based vulcanizing agent: 1 part; HVA-2: 0.5 parts; Sunlight-resistant yellow: 5 parts; The components of brominated butyl rubber, by weight, include: Brominated butyl rubber: 100 parts; BIBP: 1 copy; Triazine vulcanizing agent: 0.5 parts; HVA-2: 0.5 parts; Zinc oxide: 1 part; Stearic acid: 1 part; Magnesium oxide: 0.5 parts; Sunlight-resistant yellow: 5 parts; Brominated butyl rubber compound was dissolved in gasoline at a weight ratio of 1:2 to prepare a brominated butyl rubber slurry for later use. Fluororubber compound was dissolved in ethyl acetate at a weight ratio of 1:4 to prepare fluororubber paste for later use.
[0023] b. The adhesive tape is prepared using a coating process. A 1.5-meter wide polyester-cotton fabric is selected as the base layer. Fluororubber adhesive is first coated on one side of the base layer, with an adhesive application rate of 120g / m. 2 Then, brominated butyl rubber adhesive is coated onto the fluororubber layer, with an application rate of 50 g / m². 2 After applying a release agent (such as talc or corn starch), flip the fabric over. Then, coat the other side of the base fabric layer with brominated butyl rubber adhesive at a rate of 100 g / m². 2 .
[0024] c. Allow the rubber sheet to cool for 3 days or more until the solvent evaporates, then vulcanize it in a vulcanizing tank to obtain vulcanized rubber sheet; the vulcanization conditions are 145℃×1.5h and pressure is 0.35~0.45Mpa to obtain composite material. Example 2
[0025] A method for preparing a composite material, such as Figure 1 As shown, the steps are as follows: a. The components of the fluororubber layer, by weight, include: Fluororubber: 100 parts; Bisphenol AF: 3 parts; Accelerator BPP: 1 part; Magnesium oxide: 3 parts; Calcium hydroxide: 6 parts; Calcium oxide: 3 parts; Triazine-based vulcanizing agent: 2 parts; HVA-2: 1 part; The components of brominated butyl rubber, by weight, include: Brominated butyl rubber: 100 parts; BIBP: 1.5 copies; Triazine-based vulcanizing agent: 2 parts; HVA-2: 1 part; Zinc oxide: 1.5 parts; Stearic acid: 1.5 parts; Magnesium oxide: 0.5 parts; Sunlight-resistant yellow: 3 parts; Except for the components mentioned above, the remaining steps are completely consistent with those in Example 1, and the composite material is obtained. Example 3
[0026] A method for preparing a composite material, such as Figure 1As shown, the steps are as follows: a. The components of the fluororubber layer, by weight, include: Fluororubber: 100 parts; Bisphenol AF: 2 parts; Accelerator BPP: 0.8 parts; Magnesium oxide: 2 parts; Calcium hydroxide: 2 parts; Calcium oxide: 3 parts; Triazine vulcanizing agent: 1.5 parts; HVA-2: 1 part; Sunlight-resistant yellow: 3 parts; The components of brominated butyl rubber, by weight, include: Brominated butyl rubber: 100 parts; BIBP: 1.2 copies; Triazine vulcanizing agent: 1.5 parts; HVA-2: 1 part; Zinc oxide: 0.5 parts; Stearic acid: 0.5 parts; Magnesium oxide: 1 part; Sunlight-resistant yellow: 2 parts; Except for the components mentioned above, the remaining steps are completely consistent with those in Example 1, and the composite material is obtained.
[0027] The composite materials obtained in Examples 1-3 were processed into seam strips according to the process of cutting-sewing-bonding.
[0028] The joint strips processed in the above three embodiments were subjected to performance testing and compared with the prior art. The results are shown in the table below:
[0029] The test methods for toluene, acetone, acetonitrile, 96% sulfuric acid, 30% sodium hydroxide, and chlorine are in accordance with GB / T 23462-2009; the test methods for abrasion resistance and flexural resistance are in accordance with GB 24539-2021.
[0030] The test results above show that the prepared protective clothing has good protective performance, abrasion resistance and flexural resistance.
[0031] The scope of protection claimed by this invention is not limited to the specific embodiments described above. Moreover, for those skilled in the art, this invention can have various modifications and alterations. Any modifications, improvements, and equivalent substitutions made within the concept and principles of this invention should be included within the scope of protection of this invention.
Claims
1. A co-vulcanization system of fluororubber and brominated butyl rubber, characterized in that: Including triazine vulcanizing agents, HVA-2; The triazine vulcanizing agent is used as a co-crosslinking agent to form co-crosslinking bonds at the interface between fluororubber and brominated butyl rubber; The HVA-2 is used to adjust and match the vulcanization rate of the fluororubber and the brominated butyl rubber.
2. The co-vulcanization system of fluororubber and brominated butyl rubber according to claim 1, characterized in that: The co-vulcanization system includes a fluororubber layer and / or a brominated butyl rubber layer. In the fluororubber layer, based on 100 parts by weight of fluororubber, the amount of the triazine vulcanizing agent is 0.5 to 3 parts, and the amount of HVA-2 is 0.5 to 1.5 parts. In the brominated butyl rubber layer, based on 100 parts by weight of brominated butyl rubber, the amount of the triazine vulcanizing agent is 0.5 to 3 parts, and the amount of HVA-2 is 0.5 to 1.5 parts.
3. A composite material using the co-vulcanization system of fluororubber and brominated butyl rubber as described in any one of claims 1-2, characterized in that: It includes a base fabric layer (3), a fluororubber layer (2), and a brominated butyl rubber layer (1). The fluororubber layer (2) and the brominated butyl rubber layer (1) are co-crosslinked through a vulcanization system to achieve interfacial co-crosslinking.
4. The composite material according to claim 3, characterized in that: The components of the fluororubber layer (2) by weight include: Fluororubber: 100 parts; Bisphenol AF: 1.5–3 parts; Accelerator BPP: 0.1-1 part; Magnesium oxide: 0.5–3 parts; Calcium hydroxide: 2-6 parts; Calcium oxide: 0.5–3 parts; Triazine vulcanizing agent: 0.5–3 parts; HVA-2: 0.5–1.5 parts; The brominated butyl rubber layer (1) comprises, by weight, the following components: Brominated butyl rubber: 100 parts; BIBP: 0.5–1.5 parts; Triazine vulcanizing agent: 0.5–3 parts; HVA-2: 0.5–1.5 parts; Zinc oxide: 0.5–1.5 parts; Stearic acid: 0.5–1.5 parts; Magnesium oxide: 0.5 to 1 part.
5. The composite material according to claim 3, characterized in that: The components of the fluororubber layer (2) and the brominated butyl rubber layer (1) also include 0 to 5 parts of lightfast yellow, excluding 0 parts.
6. The composite material according to claim 3, characterized in that: The brominated butyl rubber can be replaced with chlorinated butyl rubber, and BIBP can be replaced with bis-2,5-diisopropylbenzene peroxide.
7. The composite material according to claim 3, characterized in that: The base fabric layer is made of polyester-cotton fabric, aramid fabric, nylon fabric, or polyester fabric.
8. A method for preparing a composite material as described in any one of claims 3 to 7, characterized in that, Includes the following steps: a. Mix the fluororubber layer component and the brominated butyl rubber layer component evenly to prepare brominated butyl rubber compound and fluororubber compound for later use; dissolve the brominated butyl rubber compound and the fluororubber compound in solvents to obtain fluororubber paste and brominated butyl rubber paste. b. A fluororubber layer (2) and a brominated butyl rubber layer (1) are sequentially coated on one side of the base fabric layer (3) to form a laminate; the other side is coated with a brominated butyl rubber layer (1). c. After the solvent evaporates, vulcanization is performed to obtain the composite material.
9. The method for preparing a composite material according to claim 8, characterized in that: In step a, the weight ratio of brominated butyl rubber compound to solvent gasoline is 1:2; the weight ratio of ethyl acetate solvent to fluororubber compound is 1:4; in step c, the vulcanization conditions are 145℃×1.5h and the pressure is 0.35~0.45MPa.
10. A method for preparing a composite material according to claim 8, characterized in that: Step b includes the following steps: First, apply fluororubber adhesive to one side of the base fabric layer (3), with an adhesive application rate of 120 g / m. 2 Then, brominated butyl rubber adhesive is coated onto the fluororubber layer, with an application rate of 50 g / m². 2 After applying a release agent (such as talc or corn starch), flip the fabric over. Then, coat the other side of the base fabric layer with brominated butyl rubber adhesive at a rate of 100 g / m². 2 .