WO2020113963A1 - 一种pvc焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制备方法 - Google Patents

一种pvc焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制备方法 Download PDF

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WO2020113963A1
WO2020113963A1 PCT/CN2019/096132 CN2019096132W WO2020113963A1 WO 2020113963 A1 WO2020113963 A1 WO 2020113963A1 CN 2019096132 W CN2019096132 W CN 2019096132W WO 2020113963 A1 WO2020113963 A1 WO 2020113963A1
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calcium carbonate
diluted emulsion
viscosity
nano
emulsion
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PCT/CN2019/096132
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English (en)
French (fr)
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陈晓龙
于福家
丛国龙
张淘忠
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东北大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention belongs to the technical field of materials, and particularly relates to a preparation method of nano calcium carbonate for enhancing the viscosity of a PVC weld sealing adhesive.
  • the object of the present invention is to provide a method for preparing nano-calcium carbonate for the enhancement of the viscosity of PVC weld sealing adhesives, using crystal growth and surface treatment comprehensive control and ultrasonic process strengthening to achieve nano-calcium carbonate viscosity enhancement,
  • the nano calcium carbonate with good performance can be obtained while reducing the production cost.
  • the limestone is calcined into calcium oxide at 800-1000°C, and then crushed to a particle size of S20mm to make calcium oxide fine particles; to the calcium oxide fine particles, a temperature of 95-100°C is added Digest with hot water to make Digestive slurry; the amount of hot water added is 3-6 times the mass of calcium oxide fine powder;
  • the digestive slurry is heated through a 400 mesh sieve to remove coarse particles and impurities to make a calcium hydroxide emulsion
  • a micro-bubble ultrafine calcium carbonate synthesis reactor is used as the synthesis reaction equipment; the calcium hydroxide emulsion is diluted with water to a mass concentration of 6-9% to prepare a diluted emulsion; the temperature of the diluted emulsion is reduced to S28° When C, put it in the synthesis reaction equipment, add seed crystal growth agent to the diluted emulsion; the seed crystal growth agent is sodium citrate or aluminum chloride, and the dosage of the seed crystal growth agent is 0.3 of the mass of calcium oxide fine powder ⁇ 0.8% ;
  • the mixed gas is passed into the diluted emulsion under agitation for synthesis; the conductivity and pH of the diluted emulsion are detected online during the synthesis; when the conductivity of the diluted emulsion drops to the bottom for the first time and then rises again ,
  • Add flaky growth agent to the diluted emulsion the amount of flaky growth agent accounts for 0.5 ⁇ 1% of the total mass of calcium oxide fine powder ;
  • the flaky growth agent is selected from sodium pyrophosphate and tripolyphosphate Sodium or sodium hexametaphosphate; when the pH of the diluted emulsion is at
  • the consistency enhancer uses modified sodium polyacrylate or modified starch, and the added amount is calcium oxide fine 0.5 to 1.5% of the total mass of the powder ; after the application of ultrasonic waves is completed, the mixed gas is again introduced into the
  • the reaction slurry is heated to 70 ⁇ 90°C, and then an activator is added to stir evenly for wet modification treatment to obtain an activated slurry;
  • the activator is selected from sodium carboxymethyl cellulose and modified Abietic acid or sodium stearate, the amount added is 2 ⁇ 5% of the total mass of calcium carbonate in the reaction slurry;
  • the activated slurry is filtered and dried to remove moisture, and the agglomerated part is crushed to make a PVC weld seam sealant nano calcium carbonate for viscosity enhancement.
  • the particles of the nano-calcium carbonate for the enhancement of the viscosity of the above-mentioned PVC welding seam sealing adhesive are in the form of sheets, with a particle size of 20
  • the particle size D5 (K60nm specific surface area of 30-130m 2 /g
  • the method of the present invention is used in the preparation process of PVC weld seam sealant enhanced consistency of nano calcium carbonate,
  • the growth of calcium carbonate crystals will eventually grow into ultrafine particles; when the emulsion reaches a pH value of 10.5 ⁇ 11.0, add a consistency enhancer and apply the effect of ultrasonic waves, the purpose of which is to form a
  • the layer has a complete and uniform consistency enhancement layer; adding an activator to activate the calcium carbonate, so that the prepared nano calcium carbonate has good compatibility with PVC.
  • the nano-calcium carbonate for enhancing the viscosity of the PVC weld sealant prepared by the present invention is added to the PVC weld sealant, which can not only play the role of a thickener, but also can achieve the filling effect of calcium carbonate.
  • the dual functions of thickening and filling can solve the problems of traditional nano-calcium carbonate; to evaluate the effect of nano-calcium carbonate used in PVC weld sealant on the viscosity of the finished product, can be tested by nano-calcium carbonate and plasticization
  • the rotational viscosity of the mixed emulsion (DOP) is characterized.
  • the rotational viscosity is 30 ⁇ 100P s; and under the same conditions of the present invention, the rotational viscosity can reach 200 ⁇ 400Pa-s.
  • the water used in the embodiments of the present invention is deionized water.
  • the micro-bubble ultrafine calcium carbonate synthesis reactor used in the embodiments of the present invention is the microbubble ultrafine calcium carbonate synthesis reactor in the patent of the publication number CN 204434303 U.
  • Sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate used in the embodiments of the present invention are commercially available products.
  • modified sodium polyacrylate and modified starch used in the embodiments of the present invention are commercially available products.
  • Sodium carboxymethyl cellulose, modified rosin acid and sodium stearate used in the embodiments of the present invention are commercially available products.
  • the DOP (dioctyl phthalate) used in the embodiments of the present invention is a commercially available product.
  • dilution to a mass concentration of 6-9% means that the mass concentration of calcium hydroxide is 6-9%.
  • the limestone is calcined into calcium oxide at 950°C, and then crushed to a particle size of S20mm to make calcium oxide fine particles; to the calcium oxide fine particles, hot water at a temperature of 100°C is added for digestion to prepare Into digestive slurry; the amount of hot water added is 5 times the mass of calcium oxide fine powder;
  • the digestion slurry is heated through a 400 mesh sieve to remove coarse particles and impurities to make a calcium hydroxide emulsion;
  • the micro-bubble ultrafine calcium carbonate synthesis reactor is used as the synthesis reaction equipment; the calcium hydroxide emulsion is diluted with water to a mass concentration of 6% to prepare a diluted emulsion; when the temperature of the diluted emulsion is reduced to 25°C, it is placed in In the synthesis reaction equipment, add a seed growth agent to the diluted emulsion; the seed growth agent is sodium citrate or aluminum chloride, and the amount of the seed growth agent is 0.5% of the mass of the calcium oxide fine powder;
  • the mixed gas is passed into the diluted emulsion for synthesis under stirring conditions; the conductivity and pH of the diluted emulsion are detected online during synthesis; when the conductivity of the diluted emulsion drops to the bottom for the first time and then rises again, the Add flaky growth agent to the diluted emulsion, the amount added is 0.5% of the total mass of the calcium oxide fine powder according to the flaky growth agent; the flaky growth agent is sodium pyrophosphate; when the pH of the diluted emulsion is at At 10.5, stop the mixed gas flow, add consistency enhancer to the diluted emulsion, and apply ultrasonic waves to the diluted emulsion for 10 min; the consistency enhancer is modified sodium polyacrylate, and the added amount is the total mass of calcium oxide fine powder 1.5%
  • the mixed gas is again introduced into the diluted emulsion for synthesis until the pH of the diluted emulsion drops to 7 to stop the reaction to obtain a reaction slurry; the volume percentage of carbon dioxide in the mixed gas is 80 %, and the rest is air;
  • the reaction slurry is heated to 70 ° C, and then an activator is added to stir evenly for wet modification treatment to obtain an activation material;
  • the activator is sodium carboxymethyl cellulose, the amount added is the total calcium carbonate in the reaction slurry 3% of quality;
  • the rotational viscosity of the prepared emulsion is 295 Pa-s measured by a rotational viscometer.
  • the calcination temperature of limestone is 800°C; adding hot water at a temperature of 95°C to the fine particles of calcium oxide for digestion
  • the amount of hot water added is 3 times the mass of calcium oxide fine powder
  • the calcium hydroxide emulsion is diluted with water to a mass concentration of 8%; when the temperature of the diluted emulsion is reduced to 26°C, set In the synthesis reaction equipment;
  • the seed growth agent is sodium citrate or aluminum chloride, and the dosage is 0.8% of the mass of calcium oxide fine powder;
  • flaky growth agent accounts for 0.8% of the total mass of the calcium oxide fine powder; the flaky growth agent is sodium tripolyphosphate; when the pH of the diluted emulsion is at At 10.8, stop the mixed gas flow, add the consistency enhancer to the diluted emulsion, and apply ultrasonic waves to the diluted emulsion for 15 min; the consistency enhancer is modified starch, and the added amount is 1.0% of the total mass of calcium oxide fine powder; mixed gas The volume percentage of carbon dioxide is 50%;
  • the particle size D50 of the nano-calcium carbonate for the enhancement of the viscosity of the PVC weld sealing adhesive is 52 nm, and the specific surface area is 90 m 2 /g;
  • the prepared emulsion was determined to have a rotational viscosity of 310 Pa-s by a rotational viscometer.
  • the calcination temperature of limestone is 1000°C; hot water with a temperature of 98°C is added to the calcium oxide fine particles for digestion, and the amount of hot water added is 6 times the mass of the calcium oxide fine powder;
  • the calcium hydroxide emulsion is diluted with water to a mass concentration of 9%; when the temperature of the diluted emulsion is reduced to 28°C, it is placed in a synthesis reaction device; the seed growth agent is sodium citrate or aluminum chloride, the amount is 0.3% of the mass of calcium oxide fine powder;
  • the amount of flaky growth agent is 1% of the total mass of the calcium oxide fine powder according to the flaky growth agent; the flaky growth agent is sodium hexametaphosphate; when the pH of the diluted emulsion is at At 11 o'clock, stop the mixed gas flow, add consistency enhancer to the diluted emulsion, and apply ultrasonic wave to the diluted emulsion for 20 min; the consistency enhancer is modified starch, and the added amount is 0.5% of the total mass of calcium oxide fine powder; mixed gas The volume percentage of carbon dioxide is 80%; [0045] The conductivity of the diluted emulsion when starting the synthesis is 7.7ms/cm, the conductivity is 2.6ms/cm when it first drops to the bottom, and when the conductivity rises from 2.6ms/cm to 7.7ms/cm, add Crystal thixotropic modifier

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Medicinal Preparation (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

一种PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制备方法，按以下步骤进行：（1）将石灰石煅烧后破碎，加热水消化；（2）趁热过筛；（3）加水稀释，温度降低至≤28℃时，置于合成反应设备内，加入晶种生长剂；（4）通入混合气体进行合成；当电导率第一次下降至谷底，再进行回升时，加入类片型生长剂， pH值在10.5~11时，停止通气，加入稠度强化剂并施加超声波，再次通气至pH=7；（5）加热后加入活化剂改性处理；（6）过滤烘干去除水分，将团聚的部分破碎。本发明制备的产品在PVC焊缝密封胶中添加，不仅能够起到增稠剂的作用，同时又能达到碳酸钙的填充效果。

Description

说明书
发明名称：一种 PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制 备方法
技术领域
[0001] 本发明属于材料技术领域， 特别涉及一种 PVC焊缝密封胶粘剂粘稠度增强用纳 米碳酸钙的制备方法。
背景技术
[0002] 目前汽车焊缝密封胶大多数为 PVC塑溶胶产品， 主要组成成分为基料、 填料、 增塑剂、 胶粘剂和其他辅助材料； 对于 PVC焊缝密封胶， 一方面要求涂层的硬度 、 粘结力、 伸长率、 抗剪切强度、 抗拉强度要好， 另一方面又要求其具有良好 的粘稠度； 碳酸钙粉体作为填料在 PVC焊缝密封胶中被广泛应用， 但普通碳酸钙 包括普通纳米碳酸钙作为填充剂制成的 PVC焊缝密封胶往往粘稠度低、 易流淌、 施工性能差； 解决碳酸钙粉体填充 PVC焊缝密封胶胶品粘度低的问题， 可以采用 两种措施进行调整， 一是添加专门增稠剂， 这种方法有效， 但却会增加胶品的 成本； 二是增加碳酸钙填充剂的用量， 这种方法可以一定程度提高粘稠度， 但 胶品的力学性能却难以满足要求。
发明概述
技术问题
问题的解决方案
技术解决方案
[0003] 本发明的目的是提供一种 PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制备 方法， 采用晶体生长和表面处理综合控制以及超声波过程强化， 实现纳米碳酸 钙粘稠度强化， 在降低生产成本的同时获得性能良好的纳米碳酸钙。
[0004] 本发明的方法按以下步骤进行：
[0005] 1、 将石灰石于 800~1000°C条件下煅烧成氧化钙， 然后破碎至粒径 S20mm， 制 成氧化钙细粒料； 向氧化钙细粒料中加入温度 95~100°C的热水进行消化， 制成 消化料浆； 其中热水加入量为氧化钙细粉料质量的 3~6倍；
[0006] 2、 将消化料浆趁热过 400目筛除去粗颗粒及杂质， 制成氢氧化钙乳液；
[0007] 3、 采用微泡式超微细碳酸钙合成反应器作为合成反应设备； 将氢氧化钙乳液 加水稀释至质量浓度在 6~9%， 制成稀释乳液； 在稀释乳液温度降低至 S28°C时， 置于合成反应设备内， 向稀释乳液中加入晶种生长剂； 所述的晶种生长剂选用 柠檬酸钠或氯化铝， 晶种生长剂用量为氧化钙细粉料质量的 0.3~0.8% ;
[0008] 4、 在搅拌条件下向稀释乳液中通入混合气体进行合成； 合成时在线检测稀释 乳液的电导率和 pH值； 当稀释乳液的电导率第一次下降至谷底， 再进行回升时 ， 向稀释乳液中加入类片型生长剂， 加入量按类片型生长剂占氧化钙细粉料总 质量的 0.5~1% ; 所述的类片型生长剂选用焦磷酸钠、 三聚磷酸钠或六偏磷酸钠 ; 当稀释乳液的 pH值在
Figure imgf000003_0001
时， 停止通入混合气体， 向稀释乳液中加入稠度 强化剂， 并对稀释乳液施加超声波 10~20min; 所述的稠度强化剂选用改性聚丙 烯酸钠或改性淀粉， 加入量为氧化钙细粉料总质量的 0.5~1.5% ; 施加超声波完成 后再次向稀释乳液中通入混合气体进行合成， 直至稀释乳液的 pH值降低至 7时停 止反应， 获得反应料浆； 所述的混合气体中二氧化碳的体积百分比为 30~80%， 其余为空气；
[0009] 5、 将反应料浆加热至 70~90°C， 然后加入活化剂搅拌均匀进行湿法改性处理， 获得活化料浆； 所述的活化剂选用羧甲基纤维素钠、 改性松香酸或硬脂酸钠， 加入量为反应料浆中碳酸钙总质量的 2~5% ;
[0010] 6、 将活化料浆过滤烘干去除水分， 将团聚的部分破碎， 制成 PVC焊缝密封胶 粘剂粘稠度增强用纳米碳酸钙。
[0011] 上述的 PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的颗粒为片层状， 粒径 20
〜 50nm°
[0012] 上述的 PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的粒度 D5(K60nm 比表 面积为 30~130m 2/g
发明的有益效果
有益效果
[0013] 本发明的方法路是在 PVC焊缝密封胶粘稠度增强纳米碳酸钙制备过程中， 采用 晶体生长和表面处理综合控制、 超声波过程强化的技术路线， 实现纳米碳酸钙 粘稠度强化； 纳米碳酸钙合成前后， 在反应乳液中添加晶种生长剂和类片型控 制剂的目的， 是控制碳酸钙晶体的生长， 使其最终生长成为超微细颗粒； 在乳 液达到 pH值达到 10.5~11.0时， 加入稠度强化剂， 并施加超声波的作用， 其目的 是在合成的纳米碳酸钙次表面形成一层完整均匀的稠度强化层； 加入活化剂对 碳酸钙进行活化处理， 使制备的纳米碳酸钙与 PVC具有很好的相容性。
[0014] 本发明制备的 PVC焊缝密封胶粘稠度增强用纳米碳酸钙， 在 PVC焊缝密封胶中 添加， 不仅能够起到增稠剂的作用， 同时又能达到碳酸钙的填充效果， 具有增 稠与填充双重功能， 可以很好的解决传统纳米碳酸钙存在的问题； 评价纳米碳 酸钙用于 PVC焊缝密封胶对制成产品粘稠度的影响， 可以通过检测纳米碳酸钙与 增塑剂 （DOP） 混合乳液的旋转粘度进行表征， 如一般情况下， 50g普通纳米碳 酸钙与 87.5gDOP混溶后， 旋转粘度在 30~100P s; 而本发明的在相同条件下， 旋转粘度可达 200~400Pa-s。
发明实施例
本发明的实施方式
[0015] 本发明实施例中采用的水为去离子水。
[0016] 本发明实施例中采用的微泡式超微细碳酸钙合成反应器为公开号 CN 204434303 U的专利中的微泡式超微细碳酸钙合成反应器。
[0017] 本发明实施例中采用的焦磷酸钠、 三聚磷酸钠和六偏磷酸钠为市购产品。
[0018] 本发明实施例中采用的改性聚丙烯酸钠和改性淀粉为市购产品。
[0019] 本发明实施例中采用的羧甲基纤维素钠、 改性松香酸和硬脂酸钠为市购产品。
[0020] 本发明实施例中采用的 DOP （邻苯二甲酸二辛酯） 为市购产品。
[0021] 本发明实施例中稀释至质量浓度 6~9%是指氢氧化钙的质量浓度在 6~9%。
[0022] 实施例 1
[0023] 将石灰石于 950°C条件下煅烧成氧化钙， 然后破碎至粒径 S20mm， 制成氧化钙 细粒料； 向氧化钙细粒料中加入温度 100°C的热水进行消化， 制成消化料浆； 其 中热水加入量为氧化钙细粉料质量的 5倍；
[0024] 将消化料浆趁热过 400目筛除去粗颗粒及杂质， 制成氢氧化钙乳液； [0025] 采用微泡式超微细碳酸钙合成反应器作为合成反应设备； 将氢氧化钙乳液加水 稀释至质量浓度 6%， 制成稀释乳液； 在稀释乳液温度降低至 25°C时， 置于合成 反应设备内， 向稀释乳液中加入晶种生长剂； 晶种生长剂选用柠檬酸钠或氯化 铝， 晶种生长剂用量为氧化钙细粉料质量的 0.5% ;
[0026] 在搅拌条件下向稀释乳液中通入混合气体进行合成； 合成时在线检测稀释乳液 的电导率和 pH值； 当稀释乳液的电导率第一次下降至谷底， 再进行回升时， 向 稀释乳液中加入类片型生长剂， 加入量按类片型生长剂占氧化钙细粉料总质量 的 0.5% ; 所述的类片型生长剂为焦磷酸钠； 当稀释乳液的 pH值在 10.5时， 停止 通入混合气体， 向稀释乳液中加入稠度强化剂， 并对稀释乳液施加超声波 lOmin ; 所述的稠度强化剂为改性聚丙烯酸钠， 加入量为氧化钙细粉料总质量的 1.5%
; 施加超声波完成后再次向稀释乳液中通入混合气体进行合成， 直至稀释乳液 的 pH值降低至 7时停止反应， 获得反应料浆； 混合气体中二氧化碳的体积百分比 为 80%， 其余为空气；
[0027] 其中开始进行合成时稀释乳液的电导率为 7.7ms/cm， 第一次下降到谷底时电导 率为 4.1ms/cm， 电导率从 4.1ms/cm开始向 7.7ms/cm回升时， 加入晶体触变化改性 剂；
[0028] 将反应料浆加热至 70°C， 然后加入活化剂搅拌均匀进行湿法改性处理， 获得活 化料； 活化剂为羧甲基纤维素钠， 加入量为反应料浆中碳酸钙总质量的 3% ;
[0029] 将活化料浆过滤烘干去除水分， 将团聚的部分破碎， 制成 PVC焊缝密封胶粘剂 粘稠度增强用纳米碳酸钙， 其颗粒为片层状， 粒径 20~50nm， 粒度 D50=55nm， 比表面积 30m 2/g;
[0030] PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙 50g与 87.5gDOP混合后， 所制成 的乳液经旋转粘度计测定其旋转粘度为 295Pa-s。
[0031] 实施例 2
[0032] 方法同实施例 1， 不同点在于：
[0033] ( 1) 石灰石煅烧温度 800°C; 向氧化钙细粒料中加入温度 95°C的热水进行消化
， 热水加入量为氧化钙细粉料质量的 3倍；
[0034] (2) 氢氧化钙乳液加水稀释至质量浓度 8%; 稀释乳液温度降低至 26°C时， 置 于合成反应设备内； 晶种生长剂为柠檬酸钠或氯化铝， 用量为氧化钙细粉料质 量的 0.8% ;
[0035] (3) 类片型生长剂的加入量按类片型生长剂占氧化钙细粉料总质量的 0.8% ; 类片型生长剂为三聚磷酸钠； 当稀释乳液的 pH值在 10.8时， 停止通入混合气体 ， 向稀释乳液中加入稠度强化剂， 并对稀释乳液施加超声波 15min; 稠度强化剂 为改性淀粉， 加入量为氧化钙细粉料总质量的 1.0% ; 混合气体中二氧化碳的体 积百分比为 50% ;
[0036] 开始进行合成时稀释乳液的电导率为 7.7ms/cm， 第一次下降到谷底时电导率为 3.5ms/cm, 电导率从 3.5ms/cm开始向 7.7ms/cm回升时， 加入晶体触变化改性剂
[0037] (4) 将反应料浆加热至 80°C， 加入活化剂； 活化剂为改性松香酸， 加入量为 反应料浆中碳酸钙总质量的 2% ;
[0038] (5) PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的粒度 D50=52nm， 比表面 积 90m 2/g ;
[0039] PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙 50g与 87.5gDOP混合后， 所制成 的乳液经旋转粘度计测定其旋转粘度为 310Pa-s。
[0040] 实施例 3
[0041] 方法同实施例 1， 不同点在于：
[0042] ( 1) 石灰石煅烧温度 1000°C; 向氧化钙细粒料中加入温度 98°C的热水进行消 化， 热水加入量为氧化钙细粉料质量的 6倍；
[0043] (2) 氢氧化钙乳液加水稀释至质量浓度 9%; 稀释乳液温度降低至 28°C时， 置 于合成反应设备内； 晶种生长剂为柠檬酸钠或氯化铝， 用量为氧化钙细粉料质 量的 0.3% ;
[0044] (3) 类片型生长剂的加入量按类片型生长剂占氧化钙细粉料总质量的 1%; 类 片型生长剂为六偏磷酸钠； 当稀释乳液的 pH值在 11时， 停止通入混合气体， 向 稀释乳液中加入稠度强化剂， 并对稀释乳液施加超声波 20min; 稠度强化剂为改 性淀粉， 加入量为氧化钙细粉料总质量的 0.5% ; 混合气体中二氧化碳的体积百 分比为 80% ; [0045] 开始进行合成时稀释乳液的电导率为 7.7ms/cm， 第一次下降到谷底时电导率为 2.6ms/cm, 电导率从 2.6ms/cm开始向 7.7ms/cm回升时， 加入晶体触变化改性剂
[0046] (4) 将反应料浆加热至 90°C， 加入活化剂； 活化剂为硬脂酸钠， 加入量为反 应料浆中碳酸钙总质量的 5% ;
[0047] (5) PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的粒度 D50=58nm， 比表面 积 130m 2/g; PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙 50g与 87.5gDOP混合 后， 所制成的乳液经旋转粘度计测定其旋转粘度为 245Pa-s。

Claims

权利要求书 [权利要求 1] 一种 PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制备方法， 其特 征在于按以下步骤进行：
( 1) 将石灰石于 800~1000°C条件下煅烧成氧化钙， 然后破碎至粒径 <20mm, 制成氧化钙细粒料； 向氧化钙细粒料中加入温度 95~100°C 的热水进行消化， 制成消化料浆； 其中热水加入量为氧化钙细粉料质 量的 3~6倍；
(2) 将消化料浆趁热过 400目筛除去粗颗粒及杂质， 制成氢氧化钙乳 液；
(3) 采用微泡式超微细碳酸钙合成反应器作为合成反应设备； 将氢 氧化钙乳液加水稀释至质量浓度在 6~9%， 制成稀释乳液； 在稀释乳 液温度降低至 S28°C时， 置于合成反应设备内， 向稀释乳液中加入晶 种生长剂； 所述的晶种生长剂选用柠檬酸钠或氯化铝， 晶种生长剂用 量为氧化钙细粉料质量的 0.3~0.8% ;
(4) 在搅拌条件下向稀释乳液中通入混合气体进行合成； 合成时在 线检测稀释乳液的电导率和 pH值； 当稀释乳液的电导率第一次下降 至谷底， 再进行回升时， 向稀释乳液中加入类片型生长剂， 加入量按 类片型生长剂占氧化钙细粉料总质量的 0.5~1%; 所述的类片型生长 剂选用焦磷酸钠、 三聚磷酸钠或六偏磷酸钠； 当稀释乳液的 pH值在 1 0.5~11时， 停止通入混合气体， 向稀释乳液中加入稠度强化剂， 并对 稀释乳液施加超声波 10~20min; 所述的稠度强化剂选用改性聚丙烯 酸钠或改性淀粉， 加入量为氧化钙细粉料总质量的 0.5~1.5% ; 施加超 声波完成后再次向稀释乳液中通入混合气体进行合成， 直至稀释乳液 的 pH值降低至 7时停止反应， 获得反应料浆； 所述的混合气体中二氧 化碳的体积百分比为 30~80%， 其余为空气；
(5) 将反应料浆加热至 70~90°C， 然后加入活化剂搅拌均匀进行湿法 改性处理， 获得活化料浆； 所述的活化剂选用羧甲基纤维素钠、 改性 松香酸或硬脂酸钠， 加入量为反应料浆中碳酸钙总质量的 2~5% ; (6) 将活化料浆过滤烘干去除水分， 将团聚的部分破碎， 制成 PVC 焊缝密封胶粘剂粘稠度增强用纳米碳酸钙。
[权利要求 2] 根据权利要求 1所述的 PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙 的制备方法， 其特征在于所述的 PVC焊缝密封胶粘剂粘稠度增强用纳 米碳酸钙的颗粒为片层状， 粒径 20~50nm。
[权利要求 3] 根据权利要求 1所述的 PVC焊缝密封胶粘剂粘稠度增强用纳米碳酸钙 的制备方法， 其特征在于所述的 PVC焊缝密封胶粘剂粘稠度增强用纳 米碳酸钙的粒度 D5(K60nm， 比表面积为 30~130m 2/g。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003040618A (ja) * 2001-07-26 2003-02-13 Okutama Kogyo Co Ltd 炭酸カルシウム含有複合基材、その製造方法及びそれを用いた塗工紙
CN1438279A (zh) * 2002-03-27 2003-08-27 东北大学 一种高白度纳米碳酸钙的制备方法
CN106277014A (zh) * 2016-08-04 2017-01-04 东北大学 预先分散湿法表面改性制备活性超细碳酸钙的方法
CN107986312A (zh) * 2017-12-04 2018-05-04 青州宇信钙业股份有限公司 一种高比表面积沉淀碳酸钙的制备方法
CN109370261A (zh) * 2018-12-06 2019-02-22 东北大学 一种pvc焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003040618A (ja) * 2001-07-26 2003-02-13 Okutama Kogyo Co Ltd 炭酸カルシウム含有複合基材、その製造方法及びそれを用いた塗工紙
CN1438279A (zh) * 2002-03-27 2003-08-27 东北大学 一种高白度纳米碳酸钙的制备方法
CN106277014A (zh) * 2016-08-04 2017-01-04 东北大学 预先分散湿法表面改性制备活性超细碳酸钙的方法
CN107986312A (zh) * 2017-12-04 2018-05-04 青州宇信钙业股份有限公司 一种高比表面积沉淀碳酸钙的制备方法
CN109370261A (zh) * 2018-12-06 2019-02-22 东北大学 一种pvc焊缝密封胶粘剂粘稠度增强用纳米碳酸钙的制备方法

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