阅读说明：本技术 一种原位聚合制备玻纤增强尼龙的方法及使用该方法制备的玻纤增强尼龙 (Method for preparing glass fiber reinforced nylon by in-situ polymerization and glass fiber reinforced nylon prepared by using method ) 是由 王国利 陈亚宁 陈西波 张新平 党伟荣 于 2018-07-03 设计创作，主要内容包括：本申请涉及一种原位聚合制备玻纤增强尼龙的方法、通过所述方法制备的玻纤增强尼龙以及所述玻纤增强尼龙在制备智能水表表壳中用途。所述原位聚合制备玻纤增强尼龙的方法包括以下步骤：①按照比例称取二元胺和二元酸的混合体或己内酰胺70-90重量份、玻璃纤维10-30重量份、水1-50重量份、催化剂0.1-1重量份、抗氧剂0.1-1重量份、增韧剂0.5-5重量份、润滑剂0.1-1重量份；②将各种组分加入到带有夹套盘管的高压聚合反应釜中；③进行成盐反应；④进行预聚反应；⑤进行终聚反应；⑥进行增粘反应；⑦切粒。(The application relates to a method for preparing glass fiber reinforced nylon through in-situ polymerization, the glass fiber reinforced nylon prepared through the method and application of the glass fiber reinforced nylon in preparation of a meter shell of an intelligent water meter, wherein the method for preparing the glass fiber reinforced nylon through in-situ polymerization comprises the following steps of ①, 70-90 parts by weight of a mixture of diamine and dibasic acid or caprolactam, 10-30 parts by weight of glass fiber, 1-50 parts by weight of water, 0.1-1 part by weight of a catalyst, 0.1-1 part by weight of an antioxidant, 0.5-5 parts by weight of a toughening agent and 0.1-1 part by weight of a lubricant according to a proportion, ②, adding various components into a high-pressure polymerization reaction kettle with a jacketed coil pipe, ③ carrying out salt forming reaction, ④ carrying out prepolymerization reaction, ⑤ carrying out final polymerization reaction, ⑥ carrying out tackifying reaction and ⑦ granulating.)

1. A method for preparing glass fiber reinforced nylon by in-situ polymerization comprises the following steps:

① weighing 70-90 parts by weight of a mixture of diamine and dibasic acid or caprolactam, 10-30 parts by weight of glass fiber, 1-50 parts by weight of water, 0.1-1 part by weight of catalyst, 0.1-1 part by weight of antioxidant, 0.5-5 parts by weight of flexibilizer and 0.1-1 part by weight of lubricant according to the following proportion;

② adding the components weighed according to the formula ① into a high-pressure polymerization reaction kettle with a jacketed coil, vacuumizing and replacing the air in the kettle with high-purity inert gas to control the oxygen content in the reaction kettle to be below 0.005 wt%;

③ heating the reaction temperature to 90-120 deg.C, reacting for 0.5-1 hr under the condition to perform salt-forming reaction;

④ after completing the salt-forming reaction, the reaction temperature is raised to 190-210 ℃, the pressure is between 0.6-2.0MPa, and the prepolymerization reaction is carried out for 1.5-3 hours;

⑤ after finishing the prepolymerization reaction, heating the reaction temperature to 250 ℃ and 280 ℃ and carrying out the final polymerization reaction for 2.0-4.0 hours under the pressure of 1.0-2.0 MPa;

⑥ after finishing the final polymerization reaction, the pressure in the reaction kettle is relieved to normal pressure, the reaction temperature is 250 ℃ and 280 ℃, the normal pressure reaction is carried out when the nitrogen is continuously introduced or the reaction is carried out under the condition that the vacuum degree is controlled to be about 1000Pa in absolute pressure, and the tackifying reaction is carried out for 0.5-3 hours;

⑦ after the viscosity increasing reaction is finished, the material is pulled out through a discharge valve at the bottom of the reaction kettle, and the material is cut into particles by a granulator after passing through a water tank.

2. The process according to claim 1, wherein the catalyst is selected from one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite, calcium hypophosphite, and the like.

3. The method of claim 1, wherein the antioxidant is selected from one or more of hindered phenols and phosphite compounds.

4. The method according to claim 1, wherein the catalyst is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1098, and antioxidant 1076.

5. The method of claim 1, wherein the toughening agent is selected from any one of polyolefin grafted maleic anhydride, ethylene propylene diene monomer grafted maleic anhydride, polyester elastomer, nylon elastomer and ethylene-vinyl acetate copolymer or a combination thereof.

6. The method according to claim 1, wherein the lubricant is selected from any one or more of ethylene bis stearamide, silicone powder, silicone master batch.

7. A glass fiber reinforced nylon prepared by the method for preparing the glass fiber reinforced nylon by in-situ polymerization according to any one of claims 1 to 6.

8. Use of the glass fiber reinforced nylon of claim 7 in the manufacture of a housing for a smart water meter.

Technical Field

The invention belongs to the technical field of high polymer material preparation, and particularly relates to a method for preparing glass fiber reinforced nylon through in-situ polymerization and the glass fiber reinforced nylon prepared by the method, wherein the glass fiber reinforced nylon can be used for preparing a meter shell of an intelligent water meter.

Background

A water meter is a test meter that meters the amount of water used, typically by metering the total amount of water that passes through a pipe. The inner structure of the machine can be divided into three parts, namely a shell, a sleeve and a machine core from outside to inside. At present, the shell material of the water meter is mainly made of stainless steel, brass, ball-milling cast iron, gray cast iron, plastics and other materials. For the stainless steel shell, although meeting the national drinking water sanitation requirement, the production cost is high, and the processing is not easy, so the mass production is not easy, for the brass shell, if the common brass material is used, the sanitation requirement is difficult to achieve, if the lead-free copper is adopted to prepare the water meter shell, the food certification can be passed, but the production cost is higher, in addition, the copper resource is deficient, the outdoor installation is easy to be stolen, and the current situation is not suitable for the national situation. The shell of gray cast iron is easy to corrode and rust to cause secondary pollution to water quality, and the shell of gray cast iron adopted at present has low tensile strength, poor toughness and weak corrosion resistance, is easy to break when the water meter is used according to time, and is easy to burst particularly when the temperature is low in winter. Finally, ductile iron has the advantages of high strength, good toughness and strong corrosion resistance. The cast iron is superior to grey cast iron in strength, toughness, water pressure resistance test and other aspects, but the production cost is higher.

Although the engineering plastic water meter shell generally has the problems of low mechanical strength, poor rigidity, easy aging, cold brittleness, creep deformation and the like, the product has the advantages of low cost, convenient manufacture, no toxicity, no pollution, corrosion resistance, no rusting, no scaling, light weight, sanitation and environmental protection. In 1998, the former sea water meter factory created a pioneer in China using ABS engineering plastic meter shell water meters and operated safely in low-pressure water pipe networks in Shanghai regions. However, the common engineering plastic is not suitable for areas with high pressure and severe environment, and is not popularized in a large area. Nowadays, all the world's large plastic raw material suppliers are developing new plastic materials, such as glass fiber reinforced nylon of basf, germany, which have strong mechanical strength and small creep, to compensate for the problems of common engineering plastics. The nylon water meter shell can effectively solve the problems of secondary pollution of the water meter, expensive processing of the copper shell water meter and the like, so that the research of the water meter shell material which uses plastic to replace copper and plastic strip steel becomes a necessary trend of the industrial development of the water meter.

Disclosure of Invention

In order to solve the technical defects of the existing glass fiber reinforced nylon preparation technology, the invention provides a method for preparing glass fiber reinforced nylon by in-situ polymerization.

The method for preparing the glass fiber reinforced nylon by in-situ polymerization comprises the following steps:

① weighing 70-90 parts of a mixture of diamine and diamine (wherein the molar ratio of the diamine to the diamine is 1:1) or caprolactam, 10-30 parts of glass fiber, 1-50 parts of water, 0.1-1 part of catalyst, 0.1-1 part of antioxidant, 0.5-5 parts of flexibilizer and 0.1-1 part of lubricant according to the following proportion;

② adding the components weighed according to the formula ① into a high-pressure polymerization reaction kettle with a jacketed coil, vacuumizing and replacing the air in the kettle with high-purity inert gas to control the oxygen content in the reaction kettle to be below 0.005 wt%;

③ heating the reaction temperature to 90-120 deg.C, reacting for 0.5-1 hr under the condition to perform salt-forming reaction;

④ after completing the salt-forming reaction, the reaction temperature is raised to 190-210 ℃, the pressure is between 0.6-2.0MPa, and the prepolymerization reaction is carried out for 1.5-3 hours;

⑤ after finishing the prepolymerization reaction, heating the reaction temperature to 250 ℃ and 280 ℃ and carrying out the final polymerization reaction for 2.0-4.0 hours under the pressure of 1.0-2.0 MPa;

⑥ after finishing the final polymerization reaction, the pressure in the reaction kettle is relieved to normal pressure, the reaction temperature is 250 ℃ and 280 ℃, the normal pressure reaction is carried out when the nitrogen is continuously introduced or the reaction is carried out under the condition that the vacuum degree is controlled to be about 1000Pa in absolute pressure, and the tackifying reaction is carried out for 0.5-3 hours;

⑦ after the viscosity increasing reaction is finished, the product of the invention can be obtained by discharging and bracing through a discharge valve at the bottom of the reaction kettle, and then granulating through a granulator after passing through a water tank.

In a preferred embodiment, the catalyst is selected from one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite, calcium hypophosphite, and the like.

In a preferred embodiment, the antioxidant is selected from one or more of hindered phenols and phosphite compounds, preferably from one or more of antioxidant 1010(CAS number 6683-19-8), antioxidant 168(CAS number 31570-04-4), antioxidant 1098(CAS number 23128-74-7), and antioxidant 1076(CAS number 2082-79-3).

In a preferred embodiment, the toughening agent is selected from any one of polyolefin grafted maleic anhydride (POE-g-MAH), ethylene propylene diene monomer grafted maleic anhydride (EPDM-g-MAH), polyester elastomer (TPEE), nylon elastomer (TPAE), and ethylene vinyl acetate copolymer (EVA) or a combination thereof.

In a preferred embodiment, the lubricant is selected from any one or more of ethylene bis stearamide, silicone powder, silicone master batch.

The invention also provides the glass fiber reinforced nylon prepared by the method for preparing the glass fiber reinforced nylon by in-situ polymerization.

The invention also provides application of the glass fiber reinforced nylon in preparation of a meter shell of an intelligent water meter.

Advantageous effects

The glass fiber reinforced nylon prepared according to the invention can be used for preparing a water meter shell, and compared with the traditional nylon composite material at present, on one hand, the glass fiber reinforced nylon has higher mechanical properties, particularly notch impact strength, and the overall mechanical properties are improved by more than 30%; the nylon has more excellent hydrolysis resistance, and the water absorption of the nylon is reduced; on the other hand, the compatibility of the glass fiber and the nylon is improved, the strength of the welding line is improved, the problem of fiber floating is solved, and the overall appearance of the product is good. In addition, the product has relatively low price and can meet the requirement of the industrial development of the water meter.

Detailed Description

The invention will be described in further detail, clearly and completely, with reference to specific embodiments. The examples given are only intended to illustrate the invention and do not limit it accordingly.