CN116277696A - 一种多层保温管及其生产工艺 - Google Patents

一种多层保温管及其生产工艺 Download PDF

Info

Publication number
CN116277696A
CN116277696A CN202310137949.5A CN202310137949A CN116277696A CN 116277696 A CN116277696 A CN 116277696A CN 202310137949 A CN202310137949 A CN 202310137949A CN 116277696 A CN116277696 A CN 116277696A
Authority
CN
China
Prior art keywords
heat
stirring
insulating
multilayer
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202310137949.5A
Other languages
English (en)
Other versions
CN116277696B (zh
Inventor
孙向飞
张勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei Qianhai Pipeline Manufacturing Co ltd
Original Assignee
Hebei Qianhai Pipeline Manufacturing Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei Qianhai Pipeline Manufacturing Co ltd filed Critical Hebei Qianhai Pipeline Manufacturing Co ltd
Priority to CN202310137949.5A priority Critical patent/CN116277696B/zh
Publication of CN116277696A publication Critical patent/CN116277696A/zh
Application granted granted Critical
Publication of CN116277696B publication Critical patent/CN116277696B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1228—Joining preformed parts by the expanding material
    • B29C44/1242—Joining preformed parts by the expanding material the preformed parts being concentric
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/06—Making multilayered articles
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/18—Filling preformed cavities
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • 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
    • C08K3/28—Nitrogen-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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • 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
    • C08K2003/026—Phosphorus
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

本发明公开了一种多层保温管及其生产工艺，本发明在制备一种多层保温管的过程中制备了一种发泡料，先将改性单体、PEG2000、二羟基聚二甲基硅氧烷2000、一氟一氯乙烷和保温颗粒混合，得到混合料，将混合料再与异佛尔酮二异氰酸酯混合，制得发泡料，保温颗粒是通过将红磷的多层保护，能够将内部红磷与外部完全隔绝，有效的防止了红磷受外部环境影响，保证了红磷的阻燃效果，同时与外层的水滑石复配能够很好的提升阻燃效果，并降低了燃烧时产生的烟气，同时表面的蛭石具有很好的隔热效果，进一步提升的保温管的保温效果，同外部的长链烷基能够嵌于聚氨酯分子链之间，进而提升了发泡材料的韧性，进一步提升了保温管的使用寿命。

Description

一种多层保温管及其生产工艺
技术领域
本发明涉及保温材料制备技术领域，具体涉及一种多层保温管及其生产工艺。
背景技术
保温管是绝热管道的简称，保温管用于液体、气体及其他介质的输送，在石油、化工、航天、温泉、军事、集中供热、中央空调、市政等管道的绝热工程保温，外管体和内管体之间填充保温材料的方式，来实现保温，降低热量散失的速度。但是由于管件呈圆形结构，填充的保温材料最终呈环状结构，块状硬质保温材料与软质保温材料相比，结构更稳定，但导热系数更高，保温性能略差，且保温材料多为发泡材料，遇到明火会出现快速燃烧的现象，大大增加了使用使得危险系数。
发明内容
本发明的目的在于提供一种多层保温管及其生产工艺，解决了现阶段保温管发泡材料保温效果一般，且极其易燃的问题。
本发明的目的可以通过以下技术方案实现：
一种多层保温管及其生产工艺，具体包括如下步骤：
步骤S1：将改性单体、PEG2000、二羟基聚二甲基硅氧烷2000、一氟一氯乙烷和保温颗粒加入搅拌釜中，在600-800r/min的条件下，搅拌2-3h，制得混合料；
步骤S2：将混合料像混合料中加入异佛尔酮二异氰酸酯，在转速为1000-1500r/min的条件下，搅拌10-15s，制得发泡料；
步骤S3：将工作钢管外部套设聚乙烯外套管，将发泡料在注料速度300L/min，注料压力为10-12MPa的条件下，注入工作钢管与聚乙烯外套管之间的间隙中，在50-60℃的条件下，发泡1-1.5h后，升温至80-85℃，保温10-15h，制得多层保温管。
进一步，步骤S1所述的改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为3:1:1，一氟一氯乙烷的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的5-8％，保温颗粒的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的8-10％。
进一步，步骤S2所述的异佛尔酮二异氰酸酯与改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为6:3:1:1。
进一步，所述的改性单体由如下步骤制成：
步骤A1：将4,4'-二溴甲基联苯溶于二氯甲烷中，在转速为200-300r/min，温度为40-50℃的条件下，搅拌并滴加浓硝酸，进行反应3-5h，制得中间体1，将中间体1，将中间体1、邻氯二甲苯和亚磷酸三乙酯混合均匀，通入氩气保护，在温度为158-160℃的条件下，回流反应10-15h，制得中间体2；
反应过程如下：
Figure BDA0004086583990000021
步骤A2：将中间体2、氰化钠、溴代十八烷和DMF混合均匀，通入氮气保护，在转速为200-300r/min，温度为30-40℃的条件下，进行反应4-6h，制得中间体3，将中间体3、碳酸钾水溶液和四乙基溴化铵水溶液混合均匀，在温度为100-110℃的条件下，回流3-5h，制得改性单体。
反应过程如下：
Figure BDA0004086583990000031
进一步，步骤A1所述的4,4'-二溴甲基联苯和浓硝酸的用量比为0.1mol:20mL，浓硝酸的质量分数为68％，中间体1、邻氯二甲苯和亚磷酸三乙酯的用量比为1.7mmol:12mL:3mL。
进一步，步骤A2所述的中间体2、氰化钠和溴代十八烷的摩尔比为1:3:1.5，中间体3、碳酸钾和四乙基溴化铵的用量比为30mmol:8g:1g。
进一步，所述的保温颗粒由如下步骤制成：
步骤B1：将六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水混合均匀，在转速为300-500r/min，温度为20-25℃的条件下，搅拌并加入碳酸钠溶液，调节pH值为8.5-9.5，搅拌处理1-1.5h后，升温至80-85℃，保温处理20-25h后，离心去除上清，制得包覆微囊；
步骤B2：将蛭石在温度为900-950℃的条件下，焙烧1-1.5h后，分散在去离子水中，加入KH550和甲醇，在转速为300-500r/min，温度为60-70℃的条件下，进行反应5-7h，过滤去除滤液，将滤饼分散在四氢呋喃中，加入KH560，在转速为300-500r/min，温度为30-40℃，pH值10-11的条件下，进行反应3-5h后，离心去除上清，将底物烘干，制得改性膨胀蛭石；
步骤B3：将改性膨胀蛭石、包覆微囊和乙醇混合均匀，在频率30-50kHz的条件下，超声处理20-30min后，加入去离子水，继续超声2-3h，制得复合颗粒，将复合颗粒分散在乙醚中，加入溴代十六烷和三乙胺，在转速为500-800r/min，温度为30-40℃的条件下，搅拌1-1.5h，过滤制得保温颗粒。
进一步，步骤B1所述的六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水的用量比为30mmol:10mmol:12.6g:0.06g:50mL，碳酸钠溶液的质量分数为10％。
进一步，步骤B2所述的KH550的用量为蛭石质量的5-8％，KH560与KH550的摩尔比为1:1。
进一步，步骤B3所述的改性膨胀蛭石与包覆微囊的质量比为1:8，溴代十六烷的用量为符合颗粒质量10-15％，三乙胺与溴代十六烷的摩尔比为1.1:1。
本发明的有益效果：本发明在制备一种多层保温管的过程中制备了一种发泡料，先将改性单体、PEG2000、二羟基聚二甲基硅氧烷2000、一氟一氯乙烷和保温颗粒混合，得到混合料，将混合料再与异佛尔酮二异氰酸酯混合，制得发泡料，改性单体以4,4'-二溴甲基联苯为原料用浓硝酸硝基化处理，制得中间体1，再将中间体1关环处理，制得中间体2，将中间体2与溴代十八烷反应，制得中间体3，将中间体3水解，制得改性单体，改性单体为梯形结构，在发泡料发泡产生聚氨酯分子中含有大量的改性单体与有机硅，使得制备出的发泡材料具有很好的耐热性，保温颗粒以六水合硝酸和九水合硝酸铝为原料，在红磷表面包覆一层水滑石，制得包覆微囊，再将蛭石焙烧形成膨胀蛭石，再使KH550水解并接枝在蛭石表面，使得蛭石表面接枝大量氨基，再加入KH560使得环氧基与蛭石表面的氨基反应，将改性膨胀蛭石表面的硅氧烷水解，在包覆微囊表面包覆蛭石，制得复合颗粒，将复合颗粒与溴代十六烷反应，使得溴代十六烷上溴原子位点与反应产生的羟基接枝，使得复合颗粒表面直接长链烷基，红磷的多层保护能够将内部红磷与外部完全隔绝，有效的防止了红磷受外部环境影响，保证了红磷的阻燃效果，同时与外层的水滑石复配能够很好的提升阻燃效果，并降低了燃烧时产生的烟气，同时表面的蛭石具有很好的隔热效果，进一步提升的保温管的保温效果，同外部的长链烷基能够嵌于聚氨酯分子链之间，进而提升了发泡材料的韧性，进一步提升了保温管的使用寿命。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅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作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1
一种多层保温管的生产工艺，具体包括如下步骤：
步骤S1：将改性单体、PEG2000、二羟基聚二甲基硅氧烷2000、一氟一氯乙烷和保温颗粒加入搅拌釜中，在600r/min的条件下，搅拌2h，制得混合料；
步骤S2：将混合料像混合料中加入异佛尔酮二异氰酸酯，在转速为1000r/min的条件下，搅拌10s，制得发泡料；
步骤S3：将工作钢管外部套设聚乙烯外套管，将发泡料在注料速度300L/min，注料压力为10MPa的条件下，注入工作钢管与聚乙烯外套管之间的间隙中，在50℃的条件下，发泡1h后，升温至80℃，保温10h，制得多层保温管。
步骤S1所述的改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为3:1:1，一氟一氯乙烷的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的5％，保温颗粒的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的8％。
步骤S2所述的异佛尔酮二异氰酸酯与改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为6:3:1:1。
所述的改性单体由如下步骤制成：
步骤A1：将4,4'-二溴甲基联苯溶于二氯甲烷中，在转速为200-300r/min，温度为40℃的条件下，搅拌并滴加浓硝酸，进行反应3h，制得中间体1，将中间体1，将中间体1、邻氯二甲苯和亚磷酸三乙酯混合均匀，通入氩气保护，在温度为158℃的条件下，回流反应10h，制得中间体2；
步骤A2：将中间体2、氰化钠、溴代十八烷和DMF混合均匀，通入氮气保护，在转速为200r/min，温度为30℃的条件下，进行反应4h，制得中间体3，将中间体3、碳酸钾水溶液和四乙基溴化铵水溶液混合均匀，在温度为100℃的条件下，回流3h，制得改性单体。
步骤A1所述的4,4'-二溴甲基联苯和浓硝酸的用量比为0.1mol:20mL，浓硝酸的质量分数为68％，中间体1、邻氯二甲苯和亚磷酸三乙酯的用量比为1.7mmol:12mL:3mL。
步骤A2所述的中间体2、氰化钠和溴代十八烷的摩尔比为1:3:1.5，中间体3、碳酸钾和四乙基溴化铵的用量比为30mmol:8g:1g。
所述的保温颗粒由如下步骤制成：
步骤B1：将六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水混合均匀，在转速为300r/min，温度为20℃的条件下，搅拌并加入碳酸钠溶液，调节pH值为8.5，搅拌处理1h后，升温至80℃，保温处理20h后，离心去除上清，制得包覆微囊；
步骤B2：将蛭石在温度为900℃的条件下，焙烧1h后，分散在去离子水中，加入KH550和甲醇，在转速为300r/min，温度为60℃的条件下，进行反应5h，过滤去除滤液，将滤饼分散在四氢呋喃中，加入KH560，在转速为300r/min，温度为30℃，pH值10的条件下，进行反应3h后，离心去除上清，将底物烘干，制得改性膨胀蛭石；
步骤B3：将改性膨胀蛭石、包覆微囊和乙醇混合均匀，在频率30kHz的条件下，超声处理20min后，加入去离子水，继续超声2h，制得复合颗粒，将复合颗粒分散在乙醚中，加入溴代十六烷和三乙胺，在转速为500r/min，温度为30℃的条件下，搅拌1h，过滤制得保温颗粒。
步骤B1所述的六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水的用量比为30mmol:10mmol:12.6g:0.06g:50mL，碳酸钠溶液的质量分数为10％。
步骤B2所述的KH550的用量为蛭石质量的5％，KH560与KH550的摩尔比为1:1。
步骤B3所述的改性膨胀蛭石与包覆微囊的质量比为1:8，溴代十六烷的用量为符合颗粒质量10％，三乙胺与溴代十六烷的摩尔比为1.1:1。
实施例2
一种多层保温管的生产工艺，具体包括如下步骤：
步骤S1：将改性单体、PEG2000、二羟基聚二甲基硅氧烷2000、一氟一氯乙烷和保温颗粒加入搅拌釜中，在600r/min的条件下，搅拌3h，制得混合料；
步骤S2：将混合料像混合料中加入异佛尔酮二异氰酸酯，在转速为1000r/min的条件下，搅拌10s，制得发泡料；
步骤S3：将工作钢管外部套设聚乙烯外套管，将发泡料在注料速度300L/min，注料压力为11MPa的条件下，注入工作钢管与聚乙烯外套管之间的间隙中，在55℃的条件下，发泡1.3h后，升温至80℃，保温15h，制得多层保温管。
步骤S1所述的改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为3:1:1，一氟一氯乙烷的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的7％，保温颗粒的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的9％。
步骤S2所述的异佛尔酮二异氰酸酯与改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为6:3:1:1。
所述的改性单体由如下步骤制成：
步骤A1：将4,4'-二溴甲基联苯溶于二氯甲烷中，在转速为200r/min，温度为45℃的条件下，搅拌并滴加浓硝酸，进行反应4h，制得中间体1，将中间体1，将中间体1、邻氯二甲苯和亚磷酸三乙酯混合均匀，通入氩气保护，在温度为158℃的条件下，回流反应15h，制得中间体2；
步骤A2：将中间体2、氰化钠、溴代十八烷和DMF混合均匀，通入氮气保护，在转速为200r/min，温度为35℃的条件下，进行反应5h，制得中间体3，将中间体3、碳酸钾水溶液和四乙基溴化铵水溶液混合均匀，在温度为105℃的条件下，回流4h，制得改性单体。
步骤A1所述的4,4'-二溴甲基联苯和浓硝酸的用量比为0.1mol:20mL，浓硝酸的质量分数为68％，中间体1、邻氯二甲苯和亚磷酸三乙酯的用量比为1.7mmol:12mL:3mL。
步骤A2所述的中间体2、氰化钠和溴代十八烷的摩尔比为1:3:1.5，中间体3、碳酸钾和四乙基溴化铵的用量比为30mmol:8g:1g。
所述的保温颗粒由如下步骤制成：
步骤B1：将六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水混合均匀，在转速为300r/min，温度为25℃的条件下，搅拌并加入碳酸钠溶液，调节pH值为9，搅拌处理1.5h后，升温至83℃，保温处理20h后，离心去除上清，制得包覆微囊；
步骤B2：将蛭石在温度为930℃的条件下，焙烧1.5h后，分散在去离子水中，加入KH550和甲醇，在转速为300r/min，温度为65℃的条件下，进行反应6h，过滤去除滤液，将滤饼分散在四氢呋喃中，加入KH560，在转速为500r/min，温度为35℃，pH值10的条件下，进行反应4h后，离心去除上清，将底物烘干，制得改性膨胀蛭石；
步骤B3：将改性膨胀蛭石、包覆微囊和乙醇混合均匀，在频率40kHz的条件下，超声处理25min后，加入去离子水，继续超声2.5h，制得复合颗粒，将复合颗粒分散在乙醚中，加入溴代十六烷和三乙胺，在转速为500r/min，温度为35℃的条件下，搅拌1h，过滤制得保温颗粒。
步骤B1所述的六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水的用量比为30mmol:10mmol:12.6g:0.06g:50mL，碳酸钠溶液的质量分数为10％。
步骤B2所述的KH550的用量为蛭石质量的6％，KH560与KH550的摩尔比为1:1。
步骤B3所述的改性膨胀蛭石与包覆微囊的质量比为1:8，溴代十六烷的用量为符合颗粒质量13％，三乙胺与溴代十六烷的摩尔比为1.1:1。
实施例3
一种多层保温管的生产工艺，具体包括如下步骤：
步骤S1：将改性单体、PEG2000、二羟基聚二甲基硅氧烷2000、一氟一氯乙烷和保温颗粒加入搅拌釜中，在800r/min的条件下，搅拌3h，制得混合料；
步骤S2：将混合料像混合料中加入异佛尔酮二异氰酸酯，在转速为1500r/min的条件下，搅拌15s，制得发泡料；
步骤S3：将工作钢管外部套设聚乙烯外套管，将发泡料在注料速度300L/min，注料压力为12MPa的条件下，注入工作钢管与聚乙烯外套管之间的间隙中，在60℃的条件下，发泡1.5h后，升温至85℃，保温15h，制得多层保温管。
步骤S1所述的改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为3:1:1，一氟一氯乙烷的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的8％，保温颗粒的用量为改性单体、PEG2000、二羟基聚二甲基硅氧烷2000质量和的10％。
步骤S2所述的异佛尔酮二异氰酸酯与改性单体、PEG2000、二羟基聚二甲基硅氧烷2000的摩尔比为6:3:1:1。
所述的改性单体由如下步骤制成：
步骤A1：将4,4'-二溴甲基联苯溶于二氯甲烷中，在转速为300r/min，温度为50℃的条件下，搅拌并滴加浓硝酸，进行反应5h，制得中间体1，将中间体1，将中间体1、邻氯二甲苯和亚磷酸三乙酯混合均匀，通入氩气保护，在温度为160℃的条件下，回流反应15h，制得中间体2；
步骤A2：将中间体2、氰化钠、溴代十八烷和DMF混合均匀，通入氮气保护，在转速为300r/min，温度为40℃的条件下，进行反应6h，制得中间体3，将中间体3、碳酸钾水溶液和四乙基溴化铵水溶液混合均匀，在温度为110℃的条件下，回流5h，制得改性单体。
步骤A1所述的4,4'-二溴甲基联苯和浓硝酸的用量比为0.1mol:20mL，浓硝酸的质量分数为68％，中间体1、邻氯二甲苯和亚磷酸三乙酯的用量比为1.7mmol:12mL:3mL。
步骤A2所述的中间体2、氰化钠和溴代十八烷的摩尔比为1:3:1.5，中间体3、碳酸钾和四乙基溴化铵的用量比为30mmol:8g:1g。
所述的保温颗粒由如下步骤制成：
步骤B1：将六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水混合均匀，在转速为500r/min，温度为25℃的条件下，搅拌并加入碳酸钠溶液，调节pH值为9.5，搅拌处理1.5h后，升温至85℃，保温处理25h后，离心去除上清，制得包覆微囊；
步骤B2：将蛭石在温度为950℃的条件下，焙烧1.5h后，分散在去离子水中，加入KH550和甲醇，在转速为500r/min，温度为70℃的条件下，进行反应7h，过滤去除滤液，将滤饼分散在四氢呋喃中，加入KH560，在转速为500r/min，温度为40℃，pH值11的条件下，进行反应5h后，离心去除上清，将底物烘干，制得改性膨胀蛭石；
步骤B3：将改性膨胀蛭石、包覆微囊和乙醇混合均匀，在频率50kHz的条件下，超声处理30min后，加入去离子水，继续超声3h，制得复合颗粒，将复合颗粒分散在乙醚中，加入溴代十六烷和三乙胺，在转速为800r/min，温度为40℃的条件下，搅拌1.5h，过滤制得保温颗粒。
步骤B1所述的六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水的用量比为30mmol:10mmol:12.6g:0.06g:50mL，碳酸钠溶液的质量分数为10％。
步骤B2所述的KH550的用量为蛭石质量的8％，KH560与KH550的摩尔比为1:1。
步骤B3所述的改性膨胀蛭石与包覆微囊的质量比为1:8，溴代十六烷的用量为符合颗粒质量15％，三乙胺与溴代十六烷的摩尔比为1.1:1。
对比例1
本对比例与实施例1相比用红磷代替保温颗粒，其余步骤相同。
对比例2
本对比例与实施例1相比用膨胀蛭石代替保温颗粒，其余步骤相同。
对比例3
本对比例与实施例1相比用1,4-丁二醇代替改性单体，其余步骤相同。
将实施例1-3和对比例1-3制得的发泡料发泡成型发泡密度相同，依照GB/T3399-1982的标准检测导热系数，依照GB/T2406-1993的标准检测极限氧指数，依照GB/T8627-2007的标准检测烟密度，检测结果如下：
Figure BDA0004086583990000121
由上表可知实施例1-3制得的保温管中的发泡材料具有很好的保温效果，同时阻燃效果好。
以上内容仅仅是对本发明的构思所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明的构思或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。

Claims (9)

1.一种多层保温管的生产工艺，其特征在于：具体包括如下步骤：
步骤S1：将改性单体、PEG2000、二羟基聚二甲基硅氧烷2000、一氟一氯乙烷和保温颗粒混合均匀，制得混合料；
步骤S2：将混合料像混合料中加入异佛尔酮二异氰酸酯，快速搅拌，制得发泡料；
步骤S3：将工作钢管外部套设聚乙烯外套管，将发泡料注入工作钢管与聚乙烯外套管之间的间隙中，发泡处理制得多层保温管。
2.根据权利要求1所述的一种多层保温管的生产工艺，其特征在于：所述的改性单体由如下步骤制成：
步骤A1：将4,4'-二溴甲基联苯溶于二氯甲烷中，搅拌并滴加浓硝酸，进行反应，制得中间体1，将中间体1，将中间体1、邻氯二甲苯和亚磷酸三乙酯混合回流反应，制得中间体2；
步骤A2：将中间体2、氰化钠、溴代十八烷和DMF混合反应，制得中间体3，将中间体3、碳酸钾水溶液和四乙基溴化铵水溶液混合回流反应，制得改性单体。
3.根据权利要求2所述的一种多层保温管的生产工艺，其特征在于：步骤A1所述的4,4'-二溴甲基联苯和浓硝酸的用量比为0.1mol:20mL，中间体1、邻氯二甲苯和亚磷酸三乙酯的用量比为1.7mmol:12mL:3mL。
4.根据权利要求2所述的一种多层保温管的生产工艺，其特征在于：步骤A2所述的中间体2、氰化钠和溴代十八烷的摩尔比为1:3:1.5，中间体3、碳酸钾和四乙基溴化铵的用量比为30mmo l:8g:1g。
5.根据权利要求2所述的一种多层保温管的生产工艺，其特征在于：所述的保温颗粒由如下步骤制成：
步骤B1：将六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水混合搅拌并加入碳酸钠溶液，搅拌处理后，升温保温处理，离心去除上清，制得包覆微囊；
步骤B2：将蛭石焙烧后，分散在去离子水中，加入KH550和甲醇，进行反应，过滤去除滤液，将滤饼分散在四氢呋喃中，加入KH560，进行反应，离心去除上清，将底物烘干，制得改性膨胀蛭石；
步骤B3：将改性膨胀蛭石、包覆微囊和乙醇混合均匀，超声处理后，加入去离子水，继续超声，制得复合颗粒，将复合颗粒分散在乙醚中，加入溴代十六烷和三乙胺，搅拌处理，过滤制得保温颗粒。
6.根据权利要求5所述的一种多层保温管的生产工艺，其特征在于：步骤B1所述的六水合硝酸镁、九水合硝酸铝、红磷、十二烷基苯磺酸钠和去离子水的用量比为30mmo l:10mmol:12.6g:0.06g:50mL，碳酸钠溶液的质量分数为10％。
7.根据权利要求5所述的一种多层保温管的生产工艺，其特征在于：步骤B2所述的KH550的用量为蛭石质量的5-8％，KH560与KH550的摩尔比为1:1。
8.根据权利要求5所述的一种多层保温管的生产工艺，其特征在于：步骤B3所述的改性膨胀蛭石与包覆微囊的质量比为1:8，溴代十六烷的用量为符合颗粒质量10-15％，三乙胺与溴代十六烷的摩尔比为1.1:1。
9.一种多层保温管，其特征在于：根据权利要求1-8任一所述的生产工艺生产而成。
CN202310137949.5A 2023-02-20 2023-02-20 一种多层保温管及其生产工艺 Active CN116277696B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310137949.5A CN116277696B (zh) 2023-02-20 2023-02-20 一种多层保温管及其生产工艺

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310137949.5A CN116277696B (zh) 2023-02-20 2023-02-20 一种多层保温管及其生产工艺

Publications (2)

Publication Number Publication Date
CN116277696A true CN116277696A (zh) 2023-06-23
CN116277696B CN116277696B (zh) 2023-09-22

Family

ID=86831648

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310137949.5A Active CN116277696B (zh) 2023-02-20 2023-02-20 一种多层保温管及其生产工艺

Country Status (1)

Country Link
CN (1) CN116277696B (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2040208U (zh) * 1987-09-02 1989-06-28 营口市示范消声器厂 塑料外套管式聚氨酯保温管
JPH11171802A (ja) * 1997-12-08 1999-06-29 Mikuni Seiyaku Kogyo Kk アルキルビフェニル誘導体の製造法およびその中間体
JPH11201381A (ja) * 1998-01-07 1999-07-30 Mesco Inc 凍結防止用パイプ
CN102466090A (zh) * 2010-11-10 2012-05-23 淄博高新区石桥鸿兴混凝土制品加工厂 一种新型防腐保温管
CN107383310A (zh) * 2017-07-24 2017-11-24 陈涛 一种磷化阻燃聚氨酯材料的制备方法
JP2022155370A (ja) * 2021-03-30 2022-10-13 旭有機材株式会社 難燃性発泡体用組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2040208U (zh) * 1987-09-02 1989-06-28 营口市示范消声器厂 塑料外套管式聚氨酯保温管
JPH11171802A (ja) * 1997-12-08 1999-06-29 Mikuni Seiyaku Kogyo Kk アルキルビフェニル誘導体の製造法およびその中間体
JPH11201381A (ja) * 1998-01-07 1999-07-30 Mesco Inc 凍結防止用パイプ
CN102466090A (zh) * 2010-11-10 2012-05-23 淄博高新区石桥鸿兴混凝土制品加工厂 一种新型防腐保温管
CN107383310A (zh) * 2017-07-24 2017-11-24 陈涛 一种磷化阻燃聚氨酯材料的制备方法
JP2022155370A (ja) * 2021-03-30 2022-10-13 旭有機材株式会社 難燃性発泡体用組成物

Also Published As

Publication number Publication date
CN116277696B (zh) 2023-09-22

Similar Documents

Publication Publication Date Title
CN111423728B (zh) 一种隔热复合材料及其制备方法
CN111995994B (zh) 一种采油套管用高承压堵漏剂及其加工工艺
CN108239254B (zh) 全水发泡b1级阻燃聚氨酯泡沫保温材料及其制备方法
KR100941057B1 (ko) 유리섬유 단열파이프 성형용 바인더의 제조방법
CN116277696B (zh) 一种多层保温管及其生产工艺
CN106947207A (zh) 一种轻质抑菌建筑保温材料及其制备方法
CN110669295B (zh) 一种用于输送高温流体的高耐热聚丁烯-1复合管材料制备方法
CN112646269A (zh) 一种环保高阻燃电瓶壳及其制备方法
CN107629190A (zh) 太阳能保温水箱用改性聚氨酯保温材料
CN103304351B (zh) 一种油气深井用耐高温固体推进剂及其制备方法
CN114059354B (zh) 一种基于浸渍法制备特氟龙高温布的工艺
CN101153210A (zh) 聚乙烯醇合成胶粘剂制备方法
CN103304350B (zh) 一种油气深井用耐高温固体推进剂及其制备方法
CN106497021A (zh) 聚氨酯硬泡外墙阻燃保温材料及其制备方法
CN116284665B (zh) 一种耐高温聚氨酯保温管及其制备方法
CN106565198A (zh) 一种常压干燥制备柔性二氧化硅气凝胶的方法
CN113845640B (zh) 聚氨酯泡沫塑料用聚醚多元醇及其制备方法和应用
CN113956864B (zh) 利用二氧化硅包覆的低密度高强度陶粒支撑剂及制备方法
CN115612221A (zh) 一种聚苯乙烯复合塑料及其制备方法
CN113716934A (zh) 一种柔韧性气凝胶复合绝热材料的制备工艺
CN107498967B (zh) 一种易加工保温复合材料及其制备方法
CN107353646B (zh) 一种耐热保温复合材料及其制备方法
CN101665506B (zh) 一种含硼苯乙炔基硅氧烷及其制备方法
CN107814900A (zh) 一种太阳能聚氨酯保温材料及其制备方法
CN1517374A (zh) 用于常温连续浇铸发泡的酚醛树脂的生产方法和所制成的树脂

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant