阅读说明：本技术 烯烃-苯并噁嗪共聚低聚物、交联树脂及其制备方法 (Olefin-benzoxazine co-oligomer, crosslinked resin and preparation method thereof ) 是由 鲁在君 徐利春 李家作 夏永全 衣同刚 于 2020-05-13 设计创作，主要内容包括：本发明涉及烯烃-苯并噁嗪共聚低聚物、交联树脂及其制备方法,本发明选择自由基引发剂,采用含双键的苯并噁嗪单体与二烯烃单体进行自由基二元共聚,或再添加第三单体苯乙烯进行自由基三元共聚,合成烯烃-苯并噁嗪共聚低聚物,这些共聚低聚物通过控制反应程度是可溶的。然后,再进一步加热使苯并噁嗪环发生开环反应,从而生成固化树脂,本发明在分子水平把碳氢树脂的低介电性能和聚苯并噁嗪的优异性能结合在一起,没有树脂间的相容性问题,并且可以在很大范围内调控聚二烯烃与聚并噁嗪在分子链中的组成比例,从而获得具有低介电常数、低介电损耗、高耐热性和高粘接性能的新型高分子材料。(The invention relates to olefin-benzoxazine copolymerized oligomer, cross-linked resin and a preparation method thereof, wherein a free radical initiator is selected, a double-bond benzoxazine monomer and a diene monomer are adopted for free radical binary copolymerization, or a third monomer styrene is added for free radical ternary copolymerization to synthesize the olefin-benzoxazine copolymerized oligomer, and the copolymerized oligomers are soluble by controlling the reaction degree. The invention combines the low dielectric property of hydrocarbon resin and the excellent performance of polybenzoxazine at molecular level, has no compatibility problem among resins, and can regulate and control the composition ratio of polydiene and polybenzoxazine in molecular chain in a large range, thereby obtaining the novel polymer material with low dielectric constant, low dielectric loss, high heat resistance and high adhesion performance.)

1. An olefin-benzoxazine cooligomer characterized in that: having the general formula I or II:

wherein X is 1-100, Y is 1-200, and Z is 0-200

R₁＝ -H,-CH₃,-C(CH₃)₃,-C₁₅H₃₁-n

R₂＝ -H,-CH₃

R₃＝ -C(CH₃)-,-CH₂-,-SO₂-,-O-,

2. A method for preparing an olefin-benzoxazine cooligomer, comprising the steps of:

adding an aldehyde compound, a phenolic compound and an amine compound into an organic solvent for dissolving, reacting for 4-10h at 80-120 ℃, and initiating the obtained benzoxazine monomer and an olefin monomer at 70-120 ℃ by using a free radical initiator for copolymerization to obtain the olefin-benzoxazine copolymerized oligomer.

3. The preparation method according to claim 2, wherein the aldehyde compound is one or a combination of two or more of formalin, trioxymethylene and paraformaldehyde; the amine compound is allyl amine; the phenolic compound is one or the combination of more than two of phenol, cresol, tert-butyl phenol, m-xylenol, bisphenol A, bisphenol F, bisphenol S, dicyclopentadiene phenol, catechol, hydroquinone, cardanol and dicyclopentadiene phenol.

4. The method according to claim 2, wherein the olefin monomer is one or more of isoprene, butadiene, and styrene.

5. The method according to claim 2, wherein the molar ratio of benzoxazine monomer to olefin monomer is: (5-90): (95-10).

6. The method according to claim 2, wherein the organic solvent is any one or more of acetone, butanone, cyclohexanone, toluene, xylene, diethyl ether, ethyl acetate, dioxane, chloroform, ethanol, tetrahydrofuran, dimethyl sulfoxide, and dimethylformamide.

7. The method according to claim 2, wherein the radical initiator is one or a mixture of at least two of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, hydrogen peroxide, and the like, and the amount of the radical initiator added is 0.1-10% of the total mass of the mixture.

8. An olefin-benzoxazine crosslinked resin characterized in that: having the general formula III or IV as follows:

wherein X is 1-100, Y is 1-200, and Z is 0-200

R₁＝ -H,-CH₃,-C(CH₃)₃,-C₁₅H₃₁-n

R₂＝ -H,-CH₃

R₃＝ -C(CH₃)-,-CH₂-,-SO₂-,-O-,

9. The preparation method of the benzoxazine crosslinked resin is characterized in that the benzoxazine crosslinked resin is obtained by dissolving the olefin-benzoxazine copolymerized oligomer in the formula 1 at normal temperature and then carrying out curing reaction at the temperature of 120-250 ℃ for 24-72 h.

10. The use of the benzoxazine crosslinked resin according to claim 8 as a dielectric material in the fields of high-frequency and high-speed circuit board substrates and the like.

Technical Field

The invention relates to an olefin-benzoxazine copolymerized oligomer, a crosslinked resin and a preparation method thereof, belonging to the technical field of high polymer materials.

Background

The advent of the 5G era has required the use of electronic materials and electronic devices and the like having high-frequency, high-speed and large-capacity functions for storing and transmitting signals. Therefore, the development of high-frequency copper-clad plates becomes the focus of increasing attention of people. In the high-frequency copper-clad plate, the signal transmission rate is inversely proportional to the square of the dielectric constant, and the signal loss is proportional to the square of the dielectric loss. In order to meet the requirements of 5G communication, a high molecular material with a low dielectric constant (<2.5) and a low dielectric loss (<0.005) must be used as a matrix resin of the copper-clad plate to reduce the reduction of the transmission rate and the loss of signals.

Benzoxazine is a nitrogen-containing oxa-ring structured intermediate synthesized from phenols, amine compounds and formaldehyde, and can be subjected to ring-opening polymerization under the action of heating or a catalyst to generate a cross-linked network structure polymer, which is called as polybenzoxazine or benzoxazine resin. Benzoxazine resins have many unique properties such as low water absorption, high temperature resistance, good chemical resistance, etc. Meanwhile, the benzoxazine resin has good dielectric property, relatively low dielectric constant and dielectric loss under high frequency, and particularly, the dielectric property can be kept stable in very wide frequency, so that the benzoxazine resin has wide application prospect in the field of copper clad plates. However, the dielectric constant of the traditional benzoxazine resin is generally about 3.5, the dielectric loss is about 0.02, although the traditional benzoxazine resin is superior to the traditional epoxy resin and phenolic resin, the requirement of dielectric property of 5G communication under high frequency cannot be well met, and therefore the traditional benzoxazine resin needs to be modified, and the dielectric constant and the dielectric loss are further reduced.

Polyolefins, also known as hydrocarbon resins, are low molecular weight polymers polymerized from butadiene and isoprene as the main monomers, and were first disclosed in US 5571609. The dielectric ceramic has a nonpolar molecular structure and a high degree of symmetry, so that the dielectric ceramic has excellent dielectric properties. The dielectric constant is about 2 under high frequency, the dielectric loss is less than 0.003, and the high-frequency copper clad laminate is particularly suitable for the requirements of the high-frequency copper clad laminate on the performance. However, the system mainly comprising polyolefin has low adhesion with metal and low heat resistance of resin system, which causes difficulty in subsequent processing of copper clad laminate.

Chinese patent document CN109053980A reports that polystyrene-terminated main chain benzoxazine copolymer oligomer and copolymer resin are modified by taking poly-p-vinylphenol as a phenol source end-capping agent; the obtained copolymer oligomer has a polystyrene end capping structure, and the dielectric constant and the dielectric loss of the product are slightly lower than those of polydiene because polystyrene is not of a symmetrical structure.

Chinese patent document CN104845363A adopts allyl benzoxazine resin as matrix resin, and physically blends with hydrocarbon resin, allyl polyphenylene oxide resin, and allyl modified bismaleimide resin. Although the preparation method is simple, compatibility problems between resins easily occur, and the ratio of each component cannot be adjusted in a wide range.

Therefore, there is a need to develop a modified benzoxazine resin which is free from the compatibility problem between resins and has excellent dielectric constant, dielectric loss, heat resistance and adhesive property of products.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides an olefin-benzoxazine co-oligomer which has excellent dielectric property, heat resistance and adhesive property.

The second object of the present invention is to provide an olefin-benzoxazine crosslinked resin.

Drawings

Fig. 1 is an infrared spectrum of the olefin-benzoxazine co-oligomer prepared in example 1.

FIG. 2 is a nuclear magnetic hydrogen spectrum of the olefin-benzoxazine co-oligomer prepared in example 1.

Fig. 3 is a GPC spectrum of the olefin-benzoxazine co-oligomer prepared in example 1.

FIG. 4 is a DMA spectrum of the olefin-benzoxazine cross-linked resin prepared in example 4.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.