阅读说明：本技术 赛克改性三聚氰胺甲醛树脂及其制备方法 (Cylock modified melamine formaldehyde resin and preparation method thereof ) 是由 孙明媚 王阳 杨晶巍 唐敏 唐林生 周福龙 于 2019-11-19 设计创作，主要内容包括：本专利发明了一种赛克改性三聚氰胺甲醛树脂及其制备方法。该树脂以六羟甲基三聚氰胺和赛克为原料,酸为催化剂,通过无溶剂醚化制得。具体过程如下：先将赛克加入到带加热装置的捏合机中,开启搅拌并加热至150℃,待赛克完全融化后,加入六羟甲基三聚氰胺和催化剂,并将物料加热至150℃～200℃反应1～8h,随后冷却至室温,再用粉碎机粉粹成粉末状产品。该树脂的优点在于：制备工艺简单,制备过程中基本无三废排放,产品不含氯,水溶性小,热稳定性和成炭性良好,可作为膨胀型阻燃剂的成炭剂,属于化工及高分子材料助剂领域。(The patent discloses a mosaic modified melamine formaldehyde resin and a preparation method thereof. The resin is prepared by taking hexamethylol melamine and cyco as raw materials and acid as a catalyst through solvent-free etherification. The specific process is as follows: firstly adding the mosaic into a kneader with a heating device, starting stirring and heating to 150 ℃, adding hexamethylol melamine and a catalyst after the mosaic is completely melted, heating the materials to 150-200 ℃, reacting for 1-8 h, then cooling to room temperature, and crushing into a powdery product by a crusher. The resin has the advantages that: the preparation process is simple, the three wastes are not discharged basically in the preparation process, the product does not contain chlorine, the water solubility is small, the thermal stability and the char forming property are good, and the product can be used as a char forming agent of an intumescent flame retardant, and belongs to the field of chemical industry and high polymer material additives.)

1. The preparation method of the mosaic modified melamine formaldehyde resin is characterized by comprising the following steps: firstly adding the mosaic into a kneader with a heating device, starting stirring and heating to 150 ℃, adding hexamethylol melamine and a catalyst after the mosaic is completely melted, heating the materials to 150-200 ℃, reacting for 1-8 h, then cooling to room temperature, pouring the materials out of the kneader, and crushing into a powdery product by a crusher.

2. The seek modified melamine formaldehyde resin as claimed in claim 1, wherein the mass ratio of hexamethylol melamine to the seek in the preparation method is 1.0: 1.5 to 3.0.

3. The seek modified melamine formaldehyde resin according to claim 1, wherein said catalyst is selected from the group consisting of sulfuric acid, sulfamic acid, p-toluenesulfonic acid, phosphoric acid and hydrochloric acid, and the mass ratio of hexamethylolmelamine to catalyst is 1.00: 0.01 to 0.06.

Technical Field

The invention relates to a mosaic modified melamine-formaldehyde resin and a preparation method thereof, in particular to the mosaic modified melamine-formaldehyde resin which is prepared by taking hexamethylol melamine and mosaic as raw materials and acid as a catalyst through solvent-free etherification.

Background

The Intumescent Flame Retardant (IFR) is a composite flame retardant system consisting of an acid source (dehydrating agent), a carbon source (char-forming agent) and a gas source (foaming agent), has the advantages of high flame retardant efficiency, low smoke during combustion, low toxicity of released gas and the like, meets the requirements of smoke suppression and environmental protection of the current flame retardant material, and is a green flame retardant with development potential [ Thyssal, Juniperus, Qianlun. Nevertheless, the IFR currently used has several problems, such as: (1) the flame retardant effect is still poor; (2) the IFR has poor compatibility with the polymer, and is easy to migrate to the surface of the polymer, so that various physical properties and the like of the polymer are greatly reduced; (3) the hydrolytic stability is poor, and the flame-retardant product prepared by the flame-retardant agent hardly meets the water resistance requirement; (5) the thermal stability of the polymer is remarkably reduced; (6) ammonium polyphosphate (APP), a common acid source, has poor thermal stability, and decomposed phosphoric acid is easy to corrode the die. For the above reasons, the application of IFR is also limited.

The carbon forming agent is the basis for forming an expanded carbonized layer and is one of key substances influencing the flame retardant effect of the IFR. Therefore, the development of new char-forming agents has been the focus of IFR research. The most used char-forming agents were mainly polyols such as pentaerythritol, dipentaerythritol, starch, sorbitol, etc. The carbon forming agents have high water solubility, poor compatibility with materials, easy migration and precipitation, poor carbon forming performance and thermal stability and large addition amount, so that the mechanical properties and the like of the materials are seriously reduced. These problems have severely hampered the development of IFR. In order to solve the problems, a great deal of research is carried out on the carbon forming agent at home and abroad, and a plurality of novel macromolecular carbon forming agents are developed, but the application is not many.

In recent years, the successful use of macromolecular triazine char-forming agents has significantly improved the flame retardant effect of IFR. The IFR compounded by the flame retardant and APP has the advantages that the flame retardant effect is obviously improved compared with the traditional IFR, the water resistance and the mechanical property of the flame retardant material are also obviously improved [ Wangyue, wishing and developing wisdom, Zhouxin, and the like ] the research progress of triazine series charring agents, Chinese plastics, 2018,32(2): 10-18; liuxin Xin, Qianliyun, WangJingyu, etc. the research on the charring agent in the flame-retardant material has progressed, China plastics 2015,29(11):7-16 ]. Therefore, the triazine charring agent draws wide attention at home and abroad. There are many reports on such char-forming agents. Nevertheless, such char-forming agents also have the following problems: 1) it is mainly prepared by using cyanuric chloride, monoamine (such as ethanolamine, butylamine and the like) and polyamine (such as ethylenediamine, piperazine) as raw materials through condensation and polycondensation. Because cyanuric chloride is not completely substituted, the product generally contains about 1.0 percent of chlorine, which can not completely meet the halogen-free requirement of users on the flame retardant and still has certain safety problem; 2) a large amount of waste water containing sodium chloride is generated in the production process and is difficult to treat. In addition, because a large amount of low-boiling point solvent (such as acetone) is used in the production process, the loss of the solvent is large, and serious air pollution is caused; 3) the flame retardant effect and the water resistance are still to be further improved, and the water resistance of the flame retardant material prepared by the flame retardant material can not meet the quality standards at home and abroad.

The tri (2-hydroxyethyl) isocyanurate (mosaic or THEIC for short) has good char forming effect [ Liyongqiang, Huqifen, Yangxi Wei, and the like, research on the synergistic flame retardant effect of II type ammonium polyphosphate and mosaic on polypropylene, university of Qingdao science and technology (Nature science edition), 2013,34(3): 231-; wenyan Chen, Shanshan Yuan, Yong shen, et al, effect of harbing Agent THEIC on film reducing reagents of polypropylene, j.appl.pom.sci., 2015:41214(1-8) ], but seek is a small molecule compound that is readily soluble in water and readily migrates and precipitates as a char-forming Agent. Although the problem of easy water solubility can be solved by forming derivative polyester through reaction with polybasic acid, the charring effect is not ideal [ the preparation of the said agent and its application in halogen-free flame-retardant polypropylene, 2015,31(1):27-31,37 ].

Disclosure of Invention

The inventor of the invention designs and synthesizes a novel macromolecule triazine charring agent-mosaic modified melamine formaldehyde resin according to the flame retardant mechanism of IFR and the structural characteristics of the triazine charring agent aiming at the problems of the mosaic and triazine charring agent. The main idea is to utilizeN-CH in hexamethylol melamine molecule₂The OH activity is high, and the polyether polyol is easy to etherify, and the polyether polyol is grafted to the melamine formaldehyde resin through etherification to form the polyether polyol modified melamine formaldehyde resin. The resin contains hydroxyl and triazine ring, so that the resin has both carbonizing and foaming functions.

The preparation method of the invention comprises the following steps:

(1) preparing raw materials: weighing hexamethylol melamine, mosaic and acid catalyst, wherein the mass ratio of the hexamethylol melamine to the mosaic is 1.00: 1.50-3.00: 0.01-0.06.

(2) Preparation of the mosaic modified melamine formaldehyde resin: firstly adding the mosaic into a kneader with a heating device, starting stirring and heating to 150 ℃, adding hexamethylol melamine and a catalyst after the mosaic is completely melted, heating the materials to 150-200 ℃, reacting for 1-8 h, then cooling to room temperature, pouring the materials out of the kneader, and crushing into a powdery product by a crusher.

Further, the mass ratio of hexamethylol melamine to cek is preferably 1: 1.70 to 2.5.

The catalyst is sulfuric acid, sulfamic acid, p-toluenesulfonic acid, phosphoric acid and hydrochloric acid, and the mass ratio of hexamethylolmelamine to the catalyst is preferably 1: 0.02 to 0.04.

The reaction temperature is preferably 170-190 ℃, and the reaction time is preferably 3-6 h.

The advantages of the invention are that: the preparation process is simple, the three wastes are not discharged basically in the preparation process, the product does not contain chlorine, the water solubility is small, the thermal stability and the char forming property are good, and the product can be used as the char forming agent of IFR.

Drawings

FIG. 1 is an IR spectrum of a seek modified melamine formaldehyde resin obtained in example 1 of the present invention;

FIG. 2 shows the nuclear magnetic resonance carbon spectrum (solid nuclear magnetism) of the modified melamine-formaldehyde resin obtained in example 1 of the present invention.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.

All percentages used in the present invention are mass percentages unless otherwise indicated.

Mass yield: percentage of the ratio of the mass of the product actually obtained to the sum of the masses of hexamethylolmelamine and of the added saxok.

The infrared spectrum is measured by a TENSOR-27 infrared spectrometer of Bruker, Germany, by a KBr tablet method with a wavelength scanning range of 400-^-1。

The solid nuclear magnetic resonance was measured using a nuclear magnetic resonance apparatus model DD 2600M from Agilent technologies, USA.

Thermogravimetric analysis was performed using a Q55 thermogravimetric analyzer of TA corporation, under the following test conditions: in the nitrogen atmosphere, the flow rate of the purge gas is 50mL/min, the heating rate is 10 ℃/min, the temperature range is 0-700 ℃, and the mass of the sample is 5-10 mg. The samples were dried at 150 ℃ for 2h before testing.

Determination of the solubility of the product: weighing about 2g of dried sample by using an analytical balance, placing the sample in a 250mL beaker, adding 100mL of deionized water, stirring and dissolving at 25 +/-2 ℃ for 30min, filtering, transferring a filter cake to a glass dish, and placing the glass dish in an oven to dry at 150 ℃ to constant weight. The solubility was calculated from the change in mass of the solid material before and after dissolution.

Preparation of flame-retardant PP sample: and extruding PP and IFR in a double-screw extruder (with the rotating speed of 20-30 rpm) at 190-200 ℃ according to the mass ratio of 70:30, uniformly mixing, and granulating. And (3) performing compression molding on the dried granules at 200-210 ℃ by using a tablet press under the pressure of 5MPa, then performing cold pressing under the pressure of 5MPa, and cutting the granules into sample strips with required specifications for performance testing.

And (3) testing the flame retardant property: the vertical burning test adopts an CZF-3 type horizontal vertical burning tester (Jiangning district analytical instrument factory in Nanjing) and refers to GB/T2408-1996 test, and the sample size is 100mm multiplied by 13mm multiplied by 1.6 mm.

The polypropylene (PP for short) used in the application is PPSP179 type co-polypropylene produced by Qilu division of China petrochemical company and PPH8020 homo-polypropylene produced by Lanzhou petrochemical company of China petroleum and natural gas, and the two are mixed according to the mass ratio w (PP SP179) that w (PP H8020) is 3:1 for use; insoluble ammonium polyphosphate (APP) produced by flame retardant factories of chemical companies of Shangguang Weidong; and (3) mosaic: hexamethylol melamine, produced by Yongji chemical Co., Ltd, Linyi City: manufactured by chemical limited of south china zhendong; triazine charring agent: jinan propylene bright, chemical technology, Inc.