WO2023125468A1 - 含硼树脂组合物、含硼纤维树脂复合材料及其应用 - Google Patents

含硼树脂组合物、含硼纤维树脂复合材料及其应用 Download PDF

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WO2023125468A1
WO2023125468A1 PCT/CN2022/142143 CN2022142143W WO2023125468A1 WO 2023125468 A1 WO2023125468 A1 WO 2023125468A1 CN 2022142143 W CN2022142143 W CN 2022142143W WO 2023125468 A1 WO2023125468 A1 WO 2023125468A1
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boron
resin
fiber
parts
composite material
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PCT/CN2022/142143
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English (en)
French (fr)
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刘渊豪
贡秋平
舒迪昀
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中硼(厦门)医疗器械有限公司
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Publication of WO2023125468A1 publication Critical patent/WO2023125468A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C11/00—Shielding structurally associated with the reactor
    • G21C11/02—Biological shielding ; Neutron or gamma shielding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Definitions

  • the invention relates to the field of composite materials, in particular to a boron-containing resin composition, especially a boron-containing glass fiber resin composition, which is used to prepare a boron-containing fiber resin composite material, which can be widely used in radiation in shielding material.
  • Radiotherapy such as the rapid development of boron neutron capture therapy (BNCT) technology.
  • BNCT boron neutron capture therapy
  • the purpose of the present invention is to overcome the above-mentioned problems of the prior art, to provide a kind of boron-containing resin composition, especially a kind of boron-containing glass fiber resin composition, utilize this composition to prepare and obtain boron-containing fiber resin composite material, this composite material Can be widely used in radiation shielding materials.
  • the boron-containing fiber resin composite material prepared by the boron-containing resin composition of the present invention can exhibit excellent shielding performance on the basis of maintaining very excellent mechanical properties; it can not only be used to replace conventional composite materials such as plastic plates, but also can It is used as a shielding material, such as wrapping the electronic components in the treatment room, mechanical arms, cameras and other equipment and pipelines to play an effective shielding role; it has broad application prospects.
  • the present invention provides a kind of boron-containing resin composition, and this composition comprises unsaturated polyester resin, curing agent and boron-containing substance; Based on 100 parts by weight of the unsaturated polyester resin, the The dosage of the curing agent is 0.5-5 parts, and the dosage of the boron-containing compound is 100-300 parts.
  • the curing agent is used in an amount of 0.5-2.5 parts, and the boron-containing compound is used in an amount of 180-220 parts.
  • the boron-containing resin composition of the present invention can be understood as a "raw material package" for preparing the boron-containing resin composite material, and the boron-containing resin layer material can be prepared according to the above ratio.
  • the unsaturated polyester resin includes 196 type unsaturated polyester resin, and/or is composed of 1,3-isobenzofurandione, 2,5-furandione, 2 , 2'-oxobiethanol and 1,2-propanediol polymerized unsaturated polyester resin, but not limited thereto.
  • the unsaturated polyester resin used can be obtained by monomer raw materials 1,3-isobenzofurandione, 2,5-furandione, 2,2'-oxobiethanol and 1,2 - Prepared by polymerizing propylene glycol, the molecular weight of the unsaturated polyester resin is 100-500Da, more preferably 300-500Da.
  • commercially available 196-type unsaturated polyester resin is used.
  • the CAS number of the 196-type unsaturated polyester resin is 26098-37-3, the molecular formula is C 19 H 24 O 11 , and the molecular weight is 428.387.
  • the curing agent includes a combination of one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate and methyl ethyl ketone peroxide, but not limited to this.
  • the curing agent is methyl ethyl ketone peroxide.
  • the methyl ethyl ketone peroxide used is also called peroxide-2-butanone.
  • the molecular weight is 178.21, a colorless transparent oily liquid.
  • the relative density is (15°C/4°C) 1.042. It is stable at room temperature and explodes when the temperature is higher than 100°C, with a flash point of 50°C.
  • What is actually used is 50% to 60% MEKP dimethyl phthalate solution, with a decomposition temperature of 105°C, soluble in benzene, alcohol, ether and ester, insoluble in water, and low in toxicity.
  • the boron-containing substance includes a combination of one or more of elemental boron, boric acid, borax, boron carbide and boron steel powder, but is not limited thereto.
  • the boron-containing substance is elemental boron, more preferably boron powder.
  • the composition further includes fiber material.
  • the fiber material includes a combination of one or more of glass fiber, aramid fiber, carbon fiber, polyethylene fiber and polyethylene terephthalate fiber, but Not limited to this.
  • the fiber material is glass fiber.
  • the glass fibers used are non-alkali glass fibers with a sodium oxide content of 0-2%, belonging to aluminosilicate borate glass. It has the advantages of good insulation, strong heat resistance, good corrosion resistance and high mechanical strength.
  • Commercially available glass fiber rovings can be used in the present invention.
  • the thickness of the glass fiber roving is preferably 1mm-3mm.
  • the boron-containing resin composition by adding fiber material can be used to make boron-containing fiber resin composite material, for example: fiber material can be made into fiber material resin layer, as surface setting material, on two fiber materials A boron-containing resin layer is sandwiched between the resin layers to form a boron-containing fiber resin composite material; another example: the fiber material is mixed with a boron-containing resin composition, and the boron-containing fiber resin composite material is formed by mixing and brushing for curing. Among them, the amount of fiber material is reasonably selected based on different processes.
  • composition of the present invention may also include adjuvants commonly used in the art, such as preservatives, pigments, etc., as long as there is no significant chemical reaction with the components of the present invention, they can be added and used in a conventional manner.
  • adjuvants commonly used in the art such as preservatives, pigments, etc.
  • the present invention also provides a boron-containing fiber resin composite material, the boron-containing fiber resin composite material is composed of two fiber material resin layers and a boron-containing resin layer sandwiched between the two fiber material resin layers;
  • the boron-containing resin layer is formed by stacking multiple sub-boron-containing resin layers.
  • the thickness of the fiber material resin layer is 1-7mm, preferably 3mm; the thickness of the sub-boron-containing resin layer is 1-7mm, preferably 3mm; the The number of layers of the sub-boron-containing resin layer is 2-6 layers, preferably 5 layers.
  • the preparation method of the fiber material resin layer comprises:
  • At least one layer of fiber material roving is used as the surface shaping material, and the first resin mixed colloid is layered and brushed, and the fiber material resin layer is obtained after curing.
  • the first resin mixed colloid is mixed with an unsaturated polyester resin and a curing agent in a ratio of 100:(0.5-5) parts by weight, preferably 100:2 parts by weight Get even.
  • the fiber material is glass fiber.
  • the preparation method of the boron-containing resin layer comprises:
  • the first boron-containing resin glue is applied to the fiber material resin layer by lamination, and the boron-containing resin layer is formed after curing.
  • the second resin mixed colloid adopts unsaturated polyester resin and curing agent in a ratio of 100: (0.5-5) parts by weight; more preferably, 196 type unsaturated poly
  • the ester resin and methyl ethyl ketone peroxide are uniformly mixed in a ratio of 100:2 by weight.
  • the boron-containing resin glue is laminated for 2-6 times, preferably 5 times.
  • the present invention also provides a boron-containing fiber resin composite material
  • the boron-containing fiber resin composite material is made of at least one layer of fiber material roving as a surface-setting material
  • the second boron-containing resin glue is laminated and brushed, After curing, a boron-containing fiber resin composite material is obtained.
  • the second boron-containing resin glue is a mixture of boron-containing substances and the third resin in a ratio of (100-300): (100.5-105) parts by weight, preferably 2 : 1 parts by weight and mixed uniformly.
  • the third resin mixed colloid adopts unsaturated polyester resin and curing agent in a ratio of 100: (0.5-5) parts by weight, preferably 196 type unsaturated polyester
  • the resin and methyl ethyl ketone are uniformly mixed according to the ratio of 100:1 by weight.
  • boron-containing fiber resin composite material preferably, 5 layers of fiber material roving cloth are used as surface shaping materials, and the second boron-containing resin glue is layered and brushed, and the interval between each layer of brushing is 30 minutes.
  • the fiber material is glass fiber.
  • the method of coating or brushing may, for example, be carried out by brushing with a brush specially used for coating resin glue. After painting, it is usually basically cured before the next application. Each "painting + curing" operation can obtain a sub-layer, thereby forming a laminated structure of several sub-layers.
  • the curing can be carried out by standing and solidifying naturally at room temperature, and according to specific materials, the curing can also be accelerated by ultraviolet irradiation and the like.
  • the present invention also provides the application of the boron-containing resin composite material prepared from the above-mentioned boron-containing resin composition, the above-mentioned boron-containing fiber resin composite material or the above-mentioned boron-containing fiber resin composite material as radiation shielding materials.
  • the boron-containing fiber resin composite material is used for radiation-proof cladding materials of medical device support systems (for example: medical device mechanical arms), radiation-proof shell materials for electronic equipment (for example: video monitors, cameras), and pipelines (for example: PVC pipe) Radiation-proof coating material
  • the boron-containing fiber resin composite material prepared by the composition of the present invention can show excellent shielding properties (such as shielding Rays, signals, etc.); not only can be used to replace conventional composite materials such as plastic plates, but also can be used as shielding materials, which has broad application prospects; for example, wrapping electronic components of the manipulator in the treatment room ensures the shielding protection of the manipulator The effect is of great significance to the protection of electronic components of the robotic arm in the treatment room, ensuring the quality of treatment protection in the entire treatment room.
  • Figure 1 shows the boron-containing glass fiber resin composite material prepared in Example 1 of the present invention.
  • Fig. 2 is the boron-containing glass fiber resin composite material prepared in Example 2 of the present invention.
  • Fig. 3 is a graph showing the relationship between Al activity and boron content thickness in Example 2 of the present invention.
  • This embodiment provides a boron-containing glass fiber resin composite material formed by a three-layer structure of "glass fiber resin layer + boron-containing resin layer + glass fiber resin layer” and a preparation method thereof.
  • Preparation of the resin mixed colloid mix the liquid 196 type unsaturated polyester resin and the curing agent methyl ethyl ketone peroxide according to a weight ratio of 100:2 to obtain the resin mixed colloid.
  • glass fiber roving is used as the surface shaping material, and the resin mixed colloid is laminated with a special brush; according to the curing speed and condition of the brush resin, layered brushing of the resin mixed colloid and adding glass fiber roving Gauze; specifically:
  • the thickness of the first layer of glass fiber resin layer material prepared in this embodiment is 3 mm, divided into two layers of glass fiber roving cloth, and the resin is brushed three times; after curing, the first layer of glass fiber resin layer is formed.
  • Preparation of the resin mixed colloid mix the liquid 196 type unsaturated polyester resin and the curing agent methyl ethyl ketone peroxide according to a weight ratio of 100:2 to obtain the resin mixed colloid.
  • the boron powder and the resin mixed colloid are stirred and mixed uniformly with a small mixer according to the weight ratio of 2:1 to obtain the boron-containing resin glue.
  • the thickness of the third layer of glass fiber resin layer material prepared in this embodiment is 3 mm, divided into two layers of glass fiber roving cloth, and the resin is brushed three times; the third layer of glass fiber resin layer is formed after curing.
  • the boron-containing glass fiber resin composite material of Example 1 is obtained, as shown in Figure 1, which has a three-layer structure of "glass fiber resin layer+boron-containing resin layer+glass fiber resin layer", with a thickness of 3mm+3mm ⁇ 5+3mm is 21mm in total.
  • the glass fiber resin layer needs to be based on the plasticity of the mold.
  • the thickness must be accurately controlled so as to ensure the shape of the boron-containing resin layer;
  • the boron-containing resin layer needs to ensure the ratio of resin and boron powder, and the neutron shielding thickness can only be guaranteed after fully stirring evenly (this time the boron-containing resin board is 15mm, and the effective thickness of more than 10mm needs to be guaranteed);
  • the glass fiber resin layer and the boron-containing resin layer form a sandwich relationship, and the glass fiber resin layer plays a supporting and fixing function, and achieves the mechanical properties of engineering plastics.
  • This embodiment provides a boron-containing glass fiber resin composite material obtained by "integrated molding of boron-containing glass fiber resin material” and its preparation method.
  • the method utilizes the physical properties (strength, bending resistance, brittleness, etc.) layers are added to the boron-containing resin lamination process.
  • the mixed colloid of the boron-containing resin layer needs to stand and solidify at room temperature, and cannot be solidified by heating or adding a curing agent, so as to ensure that the surface of the profile will not be severely deformed and the surface smoothness;
  • the boron-containing fiber resin composite material is used for radiation-proof cladding materials of medical device support systems (for example: medical device mechanical arms), radiation-proof shell materials for electronic equipment (for example: video monitors, cameras), and pipelines (for example: PVC pipe) radiation-proof cladding material.
  • medical device support systems for example: medical device mechanical arms
  • radiation-proof shell materials for electronic equipment for example: video monitors, cameras
  • pipelines for example: PVC pipe
  • Table 1 is a comparison table of the shielding performance and mechanical performance parameters of the boron-containing resin composite material prepared in the above two examples and the common shielding material.

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Abstract

本发明涉及复合材料领域，具体涉及一种含硼树脂组合物、含硼纤维树脂复合材料及其应用。该组合物包括不饱和聚酯类树脂、固化剂和含硼物质；以所述不饱和聚酯类树脂重量份用量为100份计，所述固化剂用量为0.5-5份，所述含硼化合物的用量为100-300份。本发明能够在保持非常优异的力学性能的基础上表现出优异的屏蔽性能；不仅能够用于替代常规的塑料板等复合材料，还能够用作屏蔽材料，例如对治疗室机械臂、摄像头及其他电子元器件进行包裹从而起到有效的屏蔽防护的作用；具有广阔的应用前景。

Description

含硼树脂组合物、含硼纤维树脂复合材料及其应用 技术领域
本发明涉及复合材料领域，具体涉及一种含硼树脂组合物，尤其是一种含硼玻璃纤维树脂组合物，利用该组合物制备获得含硼纤维树脂复合材料，该复合材料能够广泛用于辐射屏蔽材料中。
背景技术
针对癌症诊疗的技术创新与应用研发是世界科技和产业发展的重要方向。癌症治疗的一个有效手段是进行放疗，例如当前发展较快的硼中子俘获治疗(BNCT)技术。
然而以硼中子俘获治疗技术为代表的各种放疗技术都存在一个重要的问题是：放疗过程会产生大量的辐射，不仅需要医护人员做好严格的防护，给医护人员造成不便且仍存在健康风险，而且对设备环境的防护要求较高。
与放射医疗领域相类似的，其它各个领域中都存在对屏蔽材料的要求。
因此研究一种具有较好的屏蔽性能且保持较好的力学性能的新型材料是非常重要的。
发明内容
本发明的目的在于克服现有技术的上述问题，提供一种含硼树脂组合物，尤其是一种含硼玻璃纤维树脂组合物，利用该组合物制备获得含硼纤维树脂复合材料，该复合材料能够广泛用于辐射屏蔽材料中。
本发明的含硼树脂组合物制备得到的含硼纤维树脂复合材料能够在保持非常优异的力学性能的基础上表现出优异的屏蔽性能；不仅能够用于替代常规的塑料板等复合材料，还能够用作屏蔽材料，例如对治疗室电子元器件、 机械臂、摄像头等仪器设备及线路管道进行包裹从而起到有效的屏蔽防护的作用；具有广阔的应用前景。
本发明的目的通过以下技术方案得以实现：
一方面，本发明提供一种含硼树脂组合物，该组合物包括不饱和聚酯类树脂、固化剂和含硼物质；以所述不饱和聚酯类树脂重量份用量为100份计，所述固化剂用量为0.5-5份，所述含硼化合物的用量为100-300份。
上述的组合物中，优选地，以所述不饱和聚酯类树脂重量份用量为100份计，所述固化剂用量为0.5-2.5份，所述含硼化合物的用量为180-220份。
本发明含硼树脂组合物可以理解为用于制备所述含硼树脂复合材料的“原料包”，按照上述比例可以制备获得含硼树脂层材料。
上述的组合物中，优选地，所述不饱和聚酯类树脂包括196型不饱和聚酯树脂，和/或由1，3-异苯并呋喃二酮、2，5-呋喃二酮、2，2′-氧代双乙醇和1，2-丙二醇聚合得到的不饱和聚酯树脂，但不限于此。
本发明中，所采用的不饱和聚酯类树脂可以通过单体原料1，3-异苯并呋喃二酮、2，5-呋喃二酮、2，2′-氧代双乙醇和1，2-丙二醇进行聚合反应制备获得，所述不饱和聚酯类树脂的分子量为100-500Da，更优选为300-500Da。亦或采用市售的196型不饱和聚酯树脂，该196型不饱和聚酯树脂的CAS号为26098-37-3，分子式为分子式C 19H 24O 11，分子量为428.387。
上述的组合物中，优选地，所述固化剂包括过氧化环己酮、过氧化二苯甲酰、过氧化苯甲酸叔丁酯和过氧化甲乙酮中的一种或多种的组合，但不限于此。
上述的组合物中，优选地，所述固化剂为过氧化甲乙酮。
本发明中，所采用的过氧化甲乙酮又称过氧化-2-丁酮。简称MEKP，分子量为178.21，无色透明油状液体.相对密度为(15℃/4℃)1.042。室温下稳定，温度高于100℃时即发生爆炸，闪点50℃。实际使用的是50％～60％MEKP的邻苯二甲酸二甲酯溶液，分解温度105℃，溶于苯、醇、醚和 酯，不溶于水、低毒。
上述的组合物中，优选地，所述含硼物质包括单质硼、硼酸、硼砂、碳化硼和硼钢粉中的一种或多种的组合，但不限于此。
上述的组合物中，优选地，所述含硼物质为单质硼，更优选为硼粉。
上述的组合物中，优选地，所述组合物还包括纤维材料。
上述的组合物中，优选地，所述纤维材料包括玻璃纤维、芳族聚酰胺纤维、碳纤维、聚乙烯纤维和聚对苯二甲酸乙二醇酯纤维中的一种或多种的组合，但不限于此。
上述的组合物中，优选地，所述纤维材料为玻璃纤维。
本发明中，所采用的玻璃纤维为无碱玻璃纤维，其氧化钠含量为0-2％，属于铝硅硼酸盐玻璃。其具有绝缘性好、耐热性强、抗腐蚀性好，机械强度高等优点。本发明可以使用商购的玻璃纤维无捻粗纱布。所述玻璃纤维无捻粗纱布的厚度优选为1mm-3mm。
本发明的组合物中，通过添加纤维材料的含硼树脂组合物可以用来制作含硼纤维树脂复合材料，例如：纤维材料可以做成纤维材料树脂层，作为面定型材料，于两个纤维材料树脂层中间夹层含硼树脂层，形成含硼纤维树脂复合材料；再如：将纤维材料混合与含硼树脂组合物中，通过混合涂刷固化形成含硼纤维树脂复合材料。其中，纤维材料的用量根据基于不同工艺进行合理选择。
本发明的组合物还可以包括本领域常规使用的助剂，例如防腐剂、色素等，只要不与本发明的成分发生显著的化学反应，均可以按照常规的方式添加和使用。
另一方面，本发明还提供一种含硼纤维树脂复合材料，该含硼纤维树脂复合材料由两层纤维材料树脂层与夹在两层纤维材料树脂层中间的含硼树脂层组成；
所述含硼树脂层由多个子含硼树脂层层叠构成。
上述的含硼纤维树脂复合材料中，优选地，所述纤维材料树脂层的厚度为1-7mm，优选为3mm；所述子含硼树脂层的厚度为1-7mm，优选为3mm；所述子含硼树脂层的层数为2-6层，优选为5层。
上述的含硼纤维树脂复合材料中，优选地，所述纤维材料树脂层的制备方法包括：
采用至少一层纤维材料无捻粗纱布作为面定型材料，层叠涂刷第一树脂混合胶体，固化后得到纤维材料树脂层。
上述的含硼纤维树脂复合材料中，优选地，所述第一树脂混合胶体采用不饱和聚酯类树脂和固化剂按照100∶(0.5-5)重量份比例，优选100∶2重量份比例混合均匀得到。
上述的含硼纤维树脂复合材料中，优选地，所述纤维材料为玻璃纤维。
上述的含硼纤维树脂复合材料中，优选地，所述含硼树脂层的制备方法包括：
将含硼物质与第二树脂混合胶体按照(100-300)∶(100.5-105)重量份比例，优选2∶1重量份比例混合均匀得到第一含硼树脂胶；
将第一含硼树脂胶通过层叠方式涂刷至纤维材料树脂层上，固化后形成含硼树脂层。
上述的含硼纤维树脂复合材料中，优选地，所述第二树脂混合胶体采用不饱和聚酯类树脂和固化剂按照100∶(0.5-5)重量份比例；更优选采用196型不饱和聚酯树脂与过氧甲乙酮按照100∶2重量份比例混合均匀得到。
上述的含硼纤维树脂复合材料中，优选地，所述含硼树脂胶的层叠次数为2-6次，优选为5次。
在本发明中，当术语前限定有序数词时，例如第一树脂混合胶、第二树脂混合胶；这些“第一”、“第二”等词语仅用来区分不同的物料和/或不同的使用环境，而不用来限定顺序。
再一方面，本发明还提供一种含硼纤维树脂复合材料，该含硼纤维树脂 复合材料是由至少一层纤维材料无捻粗纱布作为面定型材料，层叠涂刷第二含硼树脂胶，固化后得到含硼纤维树脂复合材料。
上述的含硼纤维树脂复合材料中，优选地，所述第二含硼树脂胶是由含硼物质与第三树脂混合胶体按照(100-300)∶(100.5-105)重量份比例，优选2∶1重量份比例混合均匀得到。
上述的含硼纤维树脂复合材料中，优选地，所述第三树脂混合胶体采用不饱和聚酯类树脂和固化剂按照100∶(0.5-5)重量份比例，优选采用196型不饱和聚酯树脂与过氧甲乙酮按照100∶1重量份比例混合均匀得到。
上述的含硼纤维树脂复合材料中，优选地，采用5层纤维材料无捻粗纱布作为面定型材料，层叠涂刷第二含硼树脂胶，每层涂刷间隔30min。
上述的含硼纤维树脂复合材料中，优选地，所述纤维材料为玻璃纤维。
在本发明中，所述涂覆或涂刷的方式例如可以使用专门涂覆树脂胶的刷子进行刷涂的方式进行。涂刷后通常待基本固化后再进行下一次涂敷，每次“涂刷+固化”的操作可以得到一个子层，由此可以形成若干子层的层叠结构。
在本发明中，所述固化可以通过常温下自然静置凝固的方式进行，根据具体的材料，也可以通过紫外照射等方式加速固化。
再一方面，本发明还提供上述的含硼树脂组合物制备的含硼树脂复合材料、上述的含硼纤维树脂复合材料或上述的含硼纤维树脂复合材料作为辐射屏蔽材料中的应用。
所述含硼纤维树脂复合材料用于医疗器械支撑系统(例如：医疗器械机械臂)防辐射的包覆材料、电子设备(例如：视频监控仪、摄像机)防辐射的外壳材料、管道(例如：PVC管道)防辐射的包覆材料
本发明的有益效果：
通过上述技术方案，本发明组合物制备所得到的含硼纤维树脂复合材料能够在保持非常优异的力学性能(例如强度、韧性、抗变形能力等)的基础 上表现出优异的屏蔽性能(例如屏蔽射线、信号等)；不仅能够用于替代常规的塑料板等复合材料，还能够用作屏蔽材料，具有广阔的应用前景；例如对治疗室机械臂电子元器件进行包裹，保证了机械臂屏蔽保护效果，对治疗室机械臂电子元器件保护有极为重要的意义，确保整个治疗室的治疗防护质量。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
附图说明：
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例1制备获得的含硼玻璃纤维树脂复合材料。
图2为本发明实施例2制备获得的含硼玻璃纤维树脂复合材料。
图3为本发明实施例2中AI活度与含硼量厚度关系图。
具体实施方式
以下将通过实施例对本发明进行详细描述。本发明所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。本发明实施例中所采用的原料若无特殊说明，均为市售获得。
实施例1：
本实施例提供一种“玻璃纤维树脂层+含硼树脂层+玻璃纤维树脂层”三层结构形成的含硼玻璃纤维树脂复合材料及其制备方法。
按照如下步骤进行：
(1)第一层玻璃纤维树脂层的制备：
树脂混合胶体的制备：将液体的196型不饱和聚酯树脂与固化剂过氧甲乙酮按照100∶2重量比混合均匀得到树脂混合胶体。
在定制开模的模腔中，采用玻璃纤维无捻粗纱布作为面定型材料，使用专用刷子层叠树脂混合胶体；根据刷树脂固化速度和情况进行分层刷树脂混合胶体和添加玻璃纤维无捻粗纱布；具体为：
在定制开模的模腔中铺设一层玻璃纤维无捻粗纱，用专用刷子刷一层上述得到的树脂混合胶体，在常温下静置凝固得到第一层子层，重复刷树脂胶和凝固的步骤得到第二层子层；再次刷树玻璃纤维树脂层脂胶，并在树脂胶凝固之前再铺设一层所述玻璃纤维无捻粗纱布；由此得到一个玻璃纤维树脂材料层，其包括两层玻璃纤维无捻粗纱布和它们中间夹的三子层树脂的层叠结构。
本实施例制备的第一层玻璃纤维树脂层材料的厚度为3mm，分两层玻璃纤维无捻粗纱布，树脂分刷三次；固化后形成第一层玻璃纤维树脂层。
(2)第二层含硼树脂层的制备：
树脂混合胶体的制备：将液体的196型不饱和聚酯树脂与固化剂过氧甲乙酮按照100∶2重量比混合均匀得到树脂混合胶体。
含硼树脂胶的制备：将硼粉与树脂混合胶体按照2∶1重量比利用小型搅拌机搅拌混合均匀得到含硼树脂胶。
采用专用刷子层叠含硼树脂胶至第一层玻璃纤维树脂层上，分5次层叠，每次层叠的含硼树脂胶的厚度为3mm，每次刷完后常温下静置固化得到子含硼树脂层，重复刷含硼树脂胶，最终固化获得层叠厚度为15mm的第二层含硼树脂层。
(3)第三层玻璃纤维树脂层的制备：
在第二层含硼树脂层的表面涂刷步骤(1)中的树脂混合胶体，按照步骤(1)的方法，在第二层含硼树脂层的表面上固化形成第三层玻璃纤维树脂层。
本实施例制备的第三层玻璃纤维树脂层材料的厚度为3mm，分两层玻璃纤维无捻粗纱布，树脂分刷三次；固化后形成第三层玻璃纤维树脂层。
由此，得到本实施例1的含硼玻璃纤维树脂复合材料，如图1所示，其具有“玻璃纤维树脂层+含硼树脂层+玻璃纤维树脂层”三层结构，厚度为3mm+3mm×5+3mm共计21mm。
采用本实施例制备的含硼玻璃纤维树脂复合材料结果讨论：
(1)玻璃纤维树脂层需要依据模具塑性，在制作玻璃纤维树脂层时要准确控制厚度这样才能保证含硼树脂层的形状；
(2)含硼树脂层需保证树脂和硼粉比例，充分搅拌均匀后才能保证中子屏蔽厚度(本次含硼树脂板15mm，需保证10mm以上有效厚度)；
(3)玻璃纤维树脂层和含硼树脂层形成夹心关系，玻璃纤维树脂层起到支撑固定功能，且达到工程塑料力学属性。
实施例2：
本实施例提供一种“含硼玻璃纤维树脂材料一体成型”获得的含硼玻璃纤维树脂复合材料及其制备方法，该方法利用玻璃纤维增强材料物理属性(强度，抗弯曲力，脆性等)分层添加到含硼树脂层叠过程中。
按照如下步骤进行：
(1)树脂混合胶体的制备：将液体的196型不饱和聚酯树脂与固化剂过氧甲乙酮按照100∶1重量比混合均匀得到树脂混合胶体。
(2)含硼树脂胶的制备：将硼粉与树脂混合胶体按照2∶1重量比利用小型搅拌机搅拌混合均匀得到含硼树脂胶。
(3)采用专用刷子层叠含硼树脂胶至玻璃纤维无捻粗纱上，分5次层叠，每次层叠的含硼树脂胶的厚度为3mm，每次刷完后常温下静置30min(有利于将变形量控制在±0.5mm范围内)固化得到子含硼树脂层，重复刷含硼树脂胶，最终固化获得层叠厚度为15mm的含硼玻璃纤维树脂复合材料，如图2所示。
采用本实施例制备的含硼玻璃纤维树脂复合材料结果讨论：
(1)含硼树脂层混合胶体需要在常温下静置凝固，不能使用加热或增加固化剂方式凝固，这样才能保证型材表面不会发生严重变形，保证表面平整度；
(2)刷混合材料时间和铺设玻璃纤维布时间需要严格控制，分层叠加，刷树脂和着力要均匀才能保证面的质量和减少内部气泡；
(3)硼粉与不饱和聚酯树脂比例蒙特卡罗模拟实验：
根据AI活度与含硼量厚度关系图可以判断比例和板材厚度关系，如图3所示，根据图1曲线可知，AI饱和活度与屏蔽层厚度乘负相关走势，其中：
黄色曲线与最下方蓝色曲线降低效果最好，分别含硼比例为60％和70％；蓝色曲线70％硼粉比例太高，且与黄色曲线效果接近所以取两者中间黄金比例范围值66％，硼粉∶树脂＝2∶1；根据曲线曲率变化，屏蔽厚度在10-20mm左右，后面曲率变化率基本不变，10-15mm在对应比例内为最佳屏蔽厚度和最经济厚度。
所述含硼纤维树脂复合材料用于医疗器械支撑系统(例如：医疗器械机械臂)防辐射的包覆材料、电子设备(例如：视频监控仪、摄像机)防辐射的外壳材料、管道(例如：PVC管道)防辐射的包覆材料。
表1为上述两个实施例分别制取的含硼树脂复合材料的与普通屏蔽材料的屏蔽性能、力学性能参数的对比表。
表1：
Figure PCTCN2022142143-appb-000001
以上实施例详细描述了本发明的优选实施方式，这些实施例中的材料组分及实际均能够在保持非常优异的力学性能的基础上表现出优异的屏蔽性能，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (11)

  1. 一种含硼树脂组合物，该组合物包括不饱和聚酯类树脂、固化剂和含硼物质；以所述不饱和聚酯类树脂重量份用量为100份计，所述固化剂用量为0.5-5份，所述含硼化合物的用量为100-300份；
    优选地，以所述不饱和聚酯类树脂重量份用量为100份计，所述固化剂用量为0.5-2.5份，所述含硼化合物的用量为180-220份。
  2. 根据权利要求1所述的组合物，其中，所述不饱和聚酯类树脂包括196型不饱和聚酯树脂，和/或由1，3-异苯并呋喃二酮、2，5-呋喃二酮、2，2′-氧代双乙醇和1，2-丙二醇聚合得到的不饱和聚酯树脂。
  3. 根据权利要求1所述的组合物，其中，所述固化剂包括过氧化环己酮、过氧化二苯甲酰、过氧化苯甲酸叔丁酯和过氧化甲乙酮中的一种或多种的组合；
    优选地，所述固化剂为过氧化甲乙酮。
  4. 根据权利要求1所述的组合物，其中，所述含硼物质包括单质硼、硼酸、硼砂、碳化硼和硼钢粉中的一种或多种的组合；
    优选地，所述含硼物质为单质硼，更优选为硼粉。
  5. 根据权利要求1所述的组合物，其中，所述组合物还包括纤维材料；
    优选地，所述纤维材料包括玻璃纤维、芳族聚酰胺纤维、碳纤维、聚乙烯纤维和聚对苯二甲酸乙二醇酯纤维中的一种或多种的组合；
    更加优选地，所述纤维材料为玻璃纤维。
  6. 一种含硼纤维树脂复合材料，该含硼纤维树脂复合材料由两层纤维材料树脂层与夹在两层纤维材料树脂层中间的含硼树脂层组成；
    所述含硼树脂层由多个子含硼树脂层层叠构成；
    优选地，所述纤维材料树脂层的厚度为1-7mm，优选为3mm；所述子含硼树脂层的厚度为1-7mm，优选为3mm；所述子含硼树脂层的层数为2-6层，优选为5层。
  7. 根据权利要求6所述的含硼纤维树脂复合材料，其中，所述纤维材料树脂层的制备方法包括：
    采用至少一层纤维材料无捻粗纱布作为面定型材料，层叠涂刷第一树脂混合胶体，固化后得到纤维材料树脂层；
    优选地，所述第一树脂混合胶体采用不饱和聚酯类树脂和固化剂按照100∶(0.5-5)重量份比例，优选100∶2重量份比例混合均匀得到；
    优选地，所述纤维材料为玻璃纤维。
  8. 根据权利要求6所述的含硼纤维树脂复合材料，其中，所述含硼树脂层的制备方法包括：
    将含硼物质与第二树脂混合胶体按照(100-300)∶(100.5-105)重量份比例，优选2∶1重量份比例混合均匀得到第一含硼树脂胶；
    将第一含硼树脂胶通过层叠方式涂刷至纤维材料树脂层上，固化后形成含硼树脂层；
    优选地，所述第二树脂混合胶体采用不饱和聚酯类树脂和固化剂按照100∶(0.5-5)重量份比例；更优选采用196型不饱和聚酯树脂与过氧甲乙酮按照100∶2重量份比例混合均匀得到；
    优选地，所述含硼树脂胶的层叠次数为2-6次，优选为5次。
  9. 一种含硼纤维树脂复合材料，该含硼纤维树脂复合材料是由至少一层纤维材料无捻粗纱布作为面定型材料，层叠涂刷第二含硼树脂胶，固化后得到含硼纤维树脂复合材料；
    优选地，所述第二含硼树脂胶是由含硼物质与第三树脂混合胶体按照(100-300)∶(100.5-105)重量份比例，优选2∶1重量份比例混合均匀得到；
    优选地，所述第三树脂混合胶体采用不饱和聚酯类树脂和固化剂按照100∶(0.5-5)重量份比例，优选采用196型不饱和聚酯树脂与过氧甲乙酮按照100∶1重量份比例混合均匀得到；
    优选地，采用5层纤维材料无捻粗纱布作为面定型材料，层叠涂刷第二含硼树脂胶，每层涂刷间隔30min；
    优选地，所述纤维材料为玻璃纤维。
  10. 权利要求1-5任一项所述的含硼树脂组合物制备的含硼树脂复合材料或权利要求6-9任一项所述的含硼纤维树脂复合材料作为辐射屏蔽材料中的应用。
  11. 根据权10所述的应用，其中，所述含硼纤维树脂复合材料用于医疗器械支撑系统(例如：医疗器械机械臂)防辐射的包覆材料、电子设备(例如：视频监控仪、摄像机)防辐射的外壳材料、管道(例如：PVC管道)防辐射的包覆材料。
PCT/CN2022/142143 2021-12-31 2022-12-27 含硼树脂组合物、含硼纤维树脂复合材料及其应用 WO2023125468A1 (zh)

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