CN113462200B - 一种氨基阻聚改性导热粒子及其制备方法 - Google Patents

一种氨基阻聚改性导热粒子及其制备方法 Download PDF

Info

Publication number
CN113462200B
CN113462200B CN202110741104.8A CN202110741104A CN113462200B CN 113462200 B CN113462200 B CN 113462200B CN 202110741104 A CN202110741104 A CN 202110741104A CN 113462200 B CN113462200 B CN 113462200B
Authority
CN
China
Prior art keywords
conducting particles
modified heat
photosensitive resin
liquid photosensitive
polymerization
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.)
Active
Application number
CN202110741104.8A
Other languages
English (en)
Other versions
CN113462200A (zh
Inventor
路滕新
殷瑞雪
张楠
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.)
Benshi Intelligent Technology Development Shanghai Co ltd
Original Assignee
Benshi Intelligent Technology Development Shanghai 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 Benshi Intelligent Technology Development Shanghai Co ltd filed Critical Benshi Intelligent Technology Development Shanghai Co ltd
Priority to CN202110741104.8A priority Critical patent/CN113462200B/zh
Publication of CN113462200A publication Critical patent/CN113462200A/zh
Application granted granted Critical
Publication of CN113462200B publication Critical patent/CN113462200B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • 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
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • 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
    • C09C1/028—Compounds containing only magnesium as metal
    • 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
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • 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
    • C09C1/28—Compounds of silicon
    • 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
    • C09C1/40—Compounds of aluminium
    • 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
    • C09C3/003—Flushing
    • 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
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/043—Drying, calcination
    • 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
    • C09C3/12—Treatment with organosilicon 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2003/282—Binary compounds of nitrogen with aluminium
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Epoxy Resins (AREA)

Abstract

本发明涉及增材制造技术领域，尤其涉及一种氨基阻聚改性导热粒子及其制备方法。目前，CLIP技术必须在树脂槽底部持续通氧以及采用昂贵的透气性特氟龙薄膜才能在液态光敏树脂底部构造一层未固化液态层实现连续光固化3D打印，这种做法严重限制了CLIP技术的推广应用。基于上述问题，本发明提供一种氨基阻聚改性导热粒子，将其添加到CLIP打印用环氧树脂基液态光敏树脂中后，其会在环氧树脂基液态光敏树脂中发生沉降，最终在环氧树脂基液态光敏树脂底部形成一层盲区，盲区的氨基阻聚改性导热粒子可以中和环氧树脂基液态光敏树脂在光聚合反应中产生的质子酸，从而可以实现CLIP打印。

Description

一种氨基阻聚改性导热粒子及其制备方法
技术领域
本发明涉及增材制造技术领域，尤其涉及一种氨基阻聚改性导热粒子及其制备方法。
背景技术
3D打印技术是近年来新型的加工制造技术，具有材料利用率高、可以加工任意复杂结构以及便于实现个性化定制等优点，对传统加工制造业带来了颠覆式的影响。
面成型3D打印工艺与传统3D打印工艺通过逐点扫描堆积加工的方式不同，其可以通过依次照射实现对零件二维层面的整体成型，具有加工速度快，精度高，成本低等方面的优势，该技术的原理是在计算机的控制下，利用激光束对光敏树脂液面进行选择性照射，被照射区域树脂发生光聚合反应而固化为一个薄层，随后平台移动一个层厚的距离，进行下一层的加工直至整个零件制造完成。面成型3D打印工艺可以进一步分为两种方式实现，约束液面成型与自由液面成型，其中自由液面成型的固化层位于液面顶部，光固化反应式没有外力约束，容易产生翘曲变形，而约束液面成型的固化层位于液面底部，发生光固化反应时刮花层受到已固化部分以及树脂槽的约束，不存在变形的问题，但固化层与树脂槽分离运动中会产生受拉变形。为了解决这个问题，防粘涂层以及连续液面成型技术（CLIP）应运而生。该工艺已经被应用于牙科、个性化医疗器械、珠宝首饰、精密零件制造等众多领域。
CLIP技术是基于氧阻聚效应的3D打印技术（umbleston J R , Shirvanyants D ,Ermoshkin N , et al. Continuous liquid interface production of 3D objects[J].Science, 2015, 347(6228):1349-1352.），该技术利用美国杜邦公司发明的一种特氟龙薄膜（Teflon AF2400）和氧气来构造一层未固化液态“盲区”（dead zone），实现了快速的连续光固化3D打印。该项革命性的技术比传统SLA技术快100倍以上，有希望广泛应用于三维物体的批量化加工制造。但是由于所采用的特氟龙材料价格极其昂贵，且其透气率较低，大大限制了CLIP技术的推广应用以及打印速度的提高。
发明内容
针对现有技术中存在的问题，本发明要解决的技术问题是：目前，CLIP技术必须在树脂槽底部持续通氧以及采用昂贵的透气性特氟龙薄膜才能在液态光敏树脂底部构造一层未固化液态层实现连续光固化3D打印，这种做法严重限制了CLIP技术的推广应用。
本发明解决其技术问题所采用的技术方案是：本发明提供一种氨基阻聚改性导热粒子，按照以下方法制备：
（1）将3-氨丙基三乙氧基硅烷加入到甲苯溶剂中，搅拌均匀，得到浓度为0.06g/mL的溶液Ⅰ；
（2）将导热粒子加入到水中，搅拌均匀，得到浓度为1.42-1.43g/mL的溶液Ⅱ；
（3）溶液Ⅱ加入到溶液Ⅰ中混合均匀，使得导热粒子与3-氨丙基三乙氧基硅烷的质量比为3:10，室温下搅拌反应2h，然后对反应溶液依次进行抽滤、水洗后，置于100℃烘箱内干燥3h，即得到氨基阻聚改性导热粒子。
具体地，所述导热粒子为氧化铝、氧化镁、氧化锌、氮化铝、氮化硼、碳化硅中的一种或几种。
具体地，所述导热粒子的粒径为200nm-10μm。
具体地，所述氨基阻聚改性导热粒子可作为梯度阻聚剂添加到CLIP打印用液态光敏树脂中，所述氨基阻聚改性导热粒子可均匀沉降在所述CLIP打印用液态光敏树脂底部形成厚度为200nm-20μm的盲区。
具体地，所述的CLIP打印用液态光敏树脂为环氧树脂基液态光敏树脂。
具体地，所述环氧树脂基液态光敏树脂，以重量份数计包括以下成分：
环氧树脂 30-50份
乙烯基醚类单体 5-20份
杂环单体 5-10份
引发剂 1-5份
颜料 0.1-3份。
具体地，所述环氧树脂为 3，4-环氧环己基甲酸- 3',4'-环氧环己基甲酯、双((3,4-环氧环己基)甲基)己二酸酯、1,2-环氧-4-乙烯基环己烷中的一种或两种以上的混合物。具体地，所述乙烯基醚类单体为甲氧基乙烯、4-甲氧基苯乙烯、2-甲氧基丙-1-烯中的一种或两种以上的混合物。
具体地，所述杂环单体为氧杂环己烷、硫杂环丁烷、1,3-二氧杂环庚烷、2-氧杂环丁酮中的一种或两种以上的混合物。
具体地，所述引发剂为二苯基碘化六氟磷酸盐、二苯基碘化六氟砷酸盐、二苯基碘化六氟锑酸盐、三苯基锍六氟磷酸盐、三苯基锍六氟锑酸盐、三苯基锍三氟甲磺酸盐中的一种或两种以上的混合物。
具体地，所述颜料为钛白粉、炭黑、氧化铁红、铅铬黄、酞菁蓝或永固紫。
本发明的有益效果是：
（1）本发明获得了一种具有氧阻聚效果的氨基阻聚改性导热粒子，将其添加到CLIP打印用环氧树脂基液态光敏树脂中，在密度差的作用下，氨基阻聚改性导热粒子会在环氧树脂基液态光敏树脂中发生沉降，在树脂槽的底部形成沉降层，光固化过程中，沉降层中的氨基阻聚改性导热粒子可以中和环氧树脂基液态光敏树脂在光聚合反应中产生的质子酸，使得处于沉降层中的光敏树脂不能发生固化，最终在树脂槽底部形成一层盲区（即未固化液态层），从而可以实现CLIP打印，在这种情况下，CLIP打印不再需要在光敏树脂槽底部持续不断的通入氧气，也不再需要采用昂贵的特氟龙透气薄膜，即使将昂贵的特氟龙透气薄膜换成普通的透光离型膜也可实现连续无间断的3D打印过程，从液态光敏树脂槽中“生长”出一个三维物体；
（2）CLIP打印快速打印过程中会产生较多的热量，可以通过氨基阻聚改性导热粒子及时散失，能有效降低打印物体表面开裂的现象；
（3）本发明的方法使得CLIP打印的速度可达100-600mm/h，打印过程中基本可以忽略盲区厚度不断减薄对打印物体精度的影响。
附图说明
图1：采用本发明所制备氨基阻聚改性导热粒子进行CLIP打印过程的示意图。
图2：本发明实施例1打印的立体图。
图3：本发明实施例2打印的立体图。
图4：本发明实施例3打印的立体图。
图5：本发明实施例4打印的立体图。
图6：本发明实施例5打印的立体图。
图7：盲区厚度测定过程的示意图。
具体实施方式
现在结合实施例对本发明作进一步详细的说明。
本发明以下实施例所采用的氨基阻聚改性导热粒子，按照以下步骤获得：
（1）取3g 3-氨丙基三乙氧基硅烷加入到50mL甲苯溶剂中，搅拌均匀，得到溶液Ⅰ，
（2）将10g的导热粒子加入到7mL的水中，搅拌均匀，得到溶液Ⅱ；
（3）将溶液Ⅱ与溶液Ⅰ混合均匀，室温下搅拌反应2h，然后对反应溶液进行抽滤，水洗后，置于100℃烘箱内干燥3h，即得到氨基阻聚改性导热粒子。
本发明采用3D打印机为Carbon 3D公司制作的CLIP打印机，唯一不同之处在于，本发明将其Teflon AF2400换成了普通的透光离型膜PET膜或FEP膜。具体地，CLIP打印机的结构及原理可参见Carbon 3D公司于2015年发表的文献：umbleston J R , Shirvanyants D, Ermoshkin N , et al. Continuous liquid interface production of 3D objects[J]. Science, 2015, 347(6228):1349-1352.
打印前盲区的厚度可根据以下方法测定：
盲区的厚度可以通过在树脂槽底部，放置一块高度为100μm的金属框，在金属框内均匀铺满树脂，在金属框上面覆盖一层PP薄膜，这里所述的薄膜充当打印平台的作用，采用DLP设备在100mw光强照射下，曝光5s后，测量固化层的厚度，则液体高度和固化层厚度的差值即为盲区的厚度，这里所述的液体高度为金属框的高度，具体测定过程参见图7。
本发明对三维模型的CLIP打印，通过以下步骤实现：
（1）将Carbon 3D公司制作的CLIP打印机树脂槽底部的Teflon AF2400换成普通的PET或FEP透光离型膜。
（2）将环氧树脂基液态光敏树脂加入到3D打印机的树脂槽中，然后在环氧基液态光敏树脂中加入质量浓度为5‰-10%的氨基阻聚改性导热粒子，静置3min，使得氨基阻聚改性导热粒子在环氧基液态光敏树脂底部形成厚度为200nm-20μm的盲区；
（3）利用计算机将所要打印的三维物体CAD模型进行切片处理，得到其掩膜图像，其掩膜图像通过数字光处理成像单元处理后，可通过液态树脂槽底部的UV透射窗口向上透射形成连续的UV图像序列，以100-600mm/h的速度向上快速移动打印平台向上快速移动打印平台，即可在在打印平台的下表面得到想要打印的三维物体模型。
本发明以下实施例所采用的导热粒子为氧化铝、氧化镁、氧化锌、氮化铝、氮化硼、碳化硅中的一种或几种。
本发明以下实施例所采用的导热粒子的粒径为200nm-10μm。
本发明以下实施例所采用的环氧树脂为 3，4-环氧环己基甲酸- 3',4'-环氧环己基甲酯、双((3,4-环氧环己基)甲基)己二酸酯、1,2-环氧-4-乙烯基环己烷中的一种或两种以上的混合物。
本发明以下实施例所采用的乙烯基醚类单体为甲氧基乙烯、4-甲氧基苯乙烯、2-甲氧基丙-1-烯中的一种或两种以上的混合物。
本发明以下实施例所采用的杂环单体为氧杂环己烷、硫杂环丁烷、1,3-二氧杂环庚烷、2-氧杂环丁酮中的一种或两种以上的混合物。
本发明以下实施例所采用的引发剂为二苯基碘化六氟磷酸盐、二苯基碘化六氟砷酸盐、二苯基碘化六氟锑酸盐、三苯基锍六氟磷酸盐、三苯基锍六氟锑酸盐、三苯基锍三氟甲磺酸盐中的一种或两种以上的混合物。
本发明以下实施例所采用的颜料为钛白粉、炭黑、氧化铁红、铅铬黄、酞菁蓝或永固紫。
实施例1
采用PET透光离型膜对环氧树脂基液态光敏树脂进行3D打印，所述环氧树脂基液态光敏树脂，以重量份数计，包括以下成分：
环氧树脂 30份
乙烯基醚类单体 5份
杂环单体 5份
引发剂 1份
颜料 0.1份。
在环氧树脂基液态光敏树脂中添加有氨基阻聚改性导热粒子，氨基阻聚改性导热粒子在环氧树脂基液态光敏树脂中的质量浓度为1%，然后利用计算机将所要打印的三维物体CAD模型进行切片处理，切片厚度为0.05mm，最后200mm/h速度向上垂直移动打印平台，即得到3D打印的立体图见图2。
实施例2
采用PET透光离型膜对环氧树脂基液态光敏树脂进行3D打印，所述环氧树脂基液态光敏树脂，以重量份数计，包括以下成分：
环氧树脂 50份
乙烯基醚类单体 20份
杂环单体 10份
引发剂 5份
颜料 3份。
在环氧树脂基液态光敏树脂中添加有氨基阻聚改性导热粒子，氨基阻聚改性导热粒子在环氧树脂基液态光敏树脂中的质量浓度为1.5%，然后利用计算机将所要打印的三维物体CAD模型进行切片处理，切片厚度为0.025mm，最后100mm/h的速度向上垂直移动打印平台，即得到3D打印的立体图见图3。
实施例3
采用FEP透光离型膜对环氧树脂基液态光敏树脂进行3D打印，所述环氧树脂基液态光敏树脂，以重量份数计，包括以下成分：
环氧树脂 40份
乙烯基醚类单体 10份
杂环单体 8份
引发剂 3份
颜料 1份。
在环氧树脂基液态光敏树脂中添加有氨基阻聚改性导热粒子，氨基阻聚改性导热粒子在环氧树脂基液态光敏树脂中的质量浓度为1.5%，然后利用计算机将所要打印的三维物体CAD模型进行切片处理，切片厚度为0.1mm，最后以300mm/h的速度向上垂直移动打印平台，即得到3D打印的立体图见图4。
实施例4
采用PET透光离型膜对环氧树脂基液态光敏树脂进行3D打印，所述环氧树脂基液态光敏树脂，以重量份数计，包括以下成分：
环氧树脂 35份
乙烯基醚类单体 12份
杂环单体 6份
引发剂 3份
颜料 1.5份。
在环氧树脂基液态光敏树脂中添加有氨基阻聚改性导热粒子，氨基阻聚改性导热粒子在环氧树脂基液态光敏树脂中的质量浓度为5‰，然后利用计算机将所要打印的三维物体CAD模型进行切片处理，切片厚度为0.05mm，最后600mm/h速度向上垂直移动打印平台，即得到3D打印的立体图见图5。
实施例5
采用PET透光离型膜对环氧树脂基液态光敏树脂进行3D打印，所述环氧树脂基液态光敏树脂，以重量份数计，包括以下成分：
环氧树脂 45份
乙烯基醚类单体 17份
杂环单体 8份
引发剂 4份
颜料 2份。
在环氧树脂基液态光敏树脂中添加有氨基阻聚改性导热粒子，氨基阻聚改性导热粒子在环氧树脂基液态光敏树脂中的质量浓度为10%，然后利用计算机将所要打印的三维物体CAD模型进行切片处理，切片厚度为0.05mm，最后100mm/h速度向上垂直移动打印平台，即得到3D打印的立体图见图6。
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。

Claims (6)

1.一种氨基阻聚改性导热粒子的应用，其特征在于，所述氨基阻聚改性导热粒子按照以下方法制备：
（1）将3-氨丙基三乙氧基硅烷加入到甲苯溶剂中，搅拌均匀，得到浓度为0.06g/mL的溶液Ⅰ；
（2）将导热粒子加入到水中，搅拌均匀，得到浓度为1.42-1.43g/mL的溶液Ⅱ；
（3）溶液Ⅱ加入到溶液Ⅰ中混合均匀，使得导热粒子与3-氨丙基三乙氧基硅烷的质量比为3:10，室温下搅拌反应2h，然后对反应溶液依次进行抽滤、水洗后，置于100℃烘箱内干燥3h，即得到氨基阻聚改性导热粒子；
所述导热粒子的粒径为200nm-10μm；
所述氨基阻聚改性导热粒子可作为梯度阻聚剂添加到CLIP打印用液态光敏树脂中，所述氨基阻聚改性导热粒子可均匀沉降在所述CLIP打印用液态光敏树脂底部形成厚度为200nm-20μm的盲区；
所述的CLIP打印用液态光敏树脂为环氧树脂基液态光敏树脂；
所述环氧树脂基液态光敏树脂，以重量份数计包括以下成分：
环氧树脂 30-50份
乙烯基醚类单体 5-20份
杂环单体 5-10份
引发剂 1-5份
颜料 0.1-3份。
2.根据权利要求1所述的氨基阻聚改性导热粒子的应用，其特征在于：所述导热粒子为氧化铝、氧化镁、氧化锌、氮化铝、氮化硼、碳化硅中的一种或几种。
3.根据权利要求1所述的氨基阻聚改性导热粒子的应用，其特征在于：所述环氧树脂为3，4-环氧环己基甲酸- 3',4'-环氧环己基甲酯、双((3,4-环氧环己基)甲基)己二酸酯、1,2-环氧-4-乙烯基环己烷中的一种或两种以上的混合物。
4.根据权利要求1所述的氨基阻聚改性导热粒子的应用，其特征在于：所述乙烯基醚类单体为甲氧基乙烯、4-甲氧基苯乙烯、2-甲氧基丙-1-烯中的一种或两种以上的混合物。
5.根据权利要求1所述的氨基阻聚改性导热粒子的应用，其特征在于：所述杂环单体为氧杂环己烷、硫杂环丁烷、1,3-二氧杂环庚烷、2-氧杂环丁酮中的一种或两种以上的混合物。
6.根据权利要求1所述的氨基阻聚改性导热粒子的应用，其特征在于：所述引发剂为二苯基碘化六氟磷酸盐、二苯基碘化六氟砷酸盐、二苯基碘化六氟锑酸盐、三苯基锍六氟磷酸盐、三苯基锍六氟锑酸盐、三苯基锍三氟甲磺酸盐中的一种或两种以上的混合物。
CN202110741104.8A 2021-07-01 2021-07-01 一种氨基阻聚改性导热粒子及其制备方法 Active CN113462200B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110741104.8A CN113462200B (zh) 2021-07-01 2021-07-01 一种氨基阻聚改性导热粒子及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110741104.8A CN113462200B (zh) 2021-07-01 2021-07-01 一种氨基阻聚改性导热粒子及其制备方法

Publications (2)

Publication Number Publication Date
CN113462200A CN113462200A (zh) 2021-10-01
CN113462200B true CN113462200B (zh) 2022-05-06

Family

ID=77876974

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110741104.8A Active CN113462200B (zh) 2021-07-01 2021-07-01 一种氨基阻聚改性导热粒子及其制备方法

Country Status (1)

Country Link
CN (1) CN113462200B (zh)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807706A (zh) * 2012-07-27 2012-12-05 深圳市科聚新材料有限公司 一种聚丙烯复合材料及其制备方法
CN102876272B (zh) * 2012-09-27 2014-10-29 深圳清华大学研究院 导热粘结材料及其制备方法
CN104673160A (zh) * 2014-06-30 2015-06-03 广东丹邦科技有限公司 填充表面改性碳化硅各向同性导热胶黏剂及制备方法
CN105348867A (zh) * 2015-12-16 2016-02-24 江南大学 一种纳米氧化铝的改性方法
CN106243290B (zh) * 2016-05-11 2018-10-09 杭州乐一新材料科技有限公司 一种橡胶型光固化3d打印材料及其制备方法
CN107698722A (zh) * 2016-08-08 2018-02-16 惠展电子材料（上海）有限公司 紫外激光固化的光敏树脂及其制备方法
CN106749987A (zh) * 2016-12-12 2017-05-31 中山大简高分子材料有限公司 一种用于3d打印的sla光敏树脂组合物及其应用
CN108546393A (zh) * 2018-07-19 2018-09-18 东莞蚂蚁三维科技有限公司 一种耐超低温3d打印用光敏树脂纳米复合材料及其制备
CN112500699A (zh) * 2020-11-19 2021-03-16 裕克施乐塑料制品（太仓）有限公司 一种复合导热材料及其制备方法

Also Published As

Publication number Publication date
CN113462200A (zh) 2021-10-01

Similar Documents

Publication Publication Date Title
WO2020211656A1 (zh) 三维物体成型方法及成型装置
Zhao et al. A comparative study on 3D printed silicone-epoxy/acrylate hybrid polymers via pure photopolymerization and dual-curing mechanisms
CN102558462B (zh) 梯度组成复合材料及其制造方法
CN1307486C (zh) 聚二甲基硅氧烷微流控芯片复型光固化树脂模具制作方法
JP5975582B2 (ja) エポキシ官能性シロキサンオリゴマーを含有するエポキシ官能性の放射線硬化性組成物
KR102474841B1 (ko) 적층식 제조용 광경화성 제형의 제조
KR101572518B1 (ko) 3d 프린팅용 이중 경화형 수지 조성물을 이용한 3차원 형상의 전도체 성형물의 제조방법
CN106243290A (zh) 一种橡胶型光固化3d打印材料及其制备方法
CN103772877A (zh) 一种用于3d打印的聚苯乙烯微球改性光敏树脂及其制备方法
CN113462200B (zh) 一种氨基阻聚改性导热粒子及其制备方法
CN105754052A (zh) 一种3d打印用光固化树脂材料及其制备方法和应用
US20210223686A1 (en) High refractive index imprint compositions and materials and processes for making the same
TWI485059B (zh) Modeling method
CN110202784A (zh) 一种灰度dlp打印方法
Jenkins Rapid prototyping of PDMS devices using SU-8 lithography
CN105353587B (zh) 一种纳米压印光刻胶及其制备方法
CN113429947B (zh) 一种阻聚功能化导热粒子及其应用
CN114835900A (zh) 一种超支化聚硼硅氧烷陶瓷前驱体及其制备方法、Si-B-O-C陶瓷的制备方法
CN210477815U (zh) 3d打印系统
CN110903089A (zh) 一种采用3D打印制备的SiOC陶瓷及其制备方法
CN110261939B (zh) Pdms基双层结构磁响应微透镜阵列制造方法
CN106608952A (zh) 一种3d打印用柔性光固化树脂材料及其制备方法和应用
US20220134635A1 (en) 3d printing device, and method for preparing 3d printed structure
TWI660830B (zh) 降低光固化材料成型過程的拉拔力之方法
CN112140536B (zh) 一种高导热绝缘复合仿生树脂的数字光处理3d打印制备方法

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