CN111040718A - HMDI-based polyurethane preparation method - Google Patents

HMDI-based polyurethane preparation method Download PDF

Info

Publication number
CN111040718A
CN111040718A CN201911378300.2A CN201911378300A CN111040718A CN 111040718 A CN111040718 A CN 111040718A CN 201911378300 A CN201911378300 A CN 201911378300A CN 111040718 A CN111040718 A CN 111040718A
Authority
CN
China
Prior art keywords
hmdi
polyether glycol
polyurethane
curing agent
component
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.)
Pending
Application number
CN201911378300.2A
Other languages
Chinese (zh)
Inventor
龚文
徐庆花
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.)
Suzhou Kinglight Optoelectronics Co ltd
Original Assignee
Suzhou Kinglight Optoelectronics 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 Suzhou Kinglight Optoelectronics Co ltd filed Critical Suzhou Kinglight Optoelectronics Co ltd
Priority to CN201911378300.2A priority Critical patent/CN111040718A/en
Publication of CN111040718A publication Critical patent/CN111040718A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to the technical field of electronic device packaging materials, and particularly relates to a polyurethane preparation method based on HMDI. Firstly, HMDI is used as a raw material to prepare a curing agent prepolymer, and the formula is as follows: HMDI: polyether glycol (Mn 1000), polyether glycol (Mn 2000): polyether glycol (Mn ═ 3000): phenol: DOP ═ 1: 0.5: 0.5: 0.05: 1: a molar ratio of 0.01; then according to the prepolymer of the curing agent: solvent: filling: pigment: leveling agent 100: 90: 115: 15: 5, preparing a component A; then according to the curing agent: solvent: filling: pigment: deblocking accelerator 100: 70: 220: 10: 10 to prepare a component B; finally A, B components were mixed according to A: b is 10: 1, and then uniformly mixing to prepare the polyurethane packaging adhesive. The method can be used for preparing the environment-friendly, nontoxic and harmless polyurethane packaging adhesive which can be cured at room temperature.

Description

HMDI-based polyurethane preparation method
Technical Field
The invention belongs to the technical field of electronic device packaging materials, and particularly relates to a polyurethane preparation method based on HMDI.
Background
With the increasing demand of commercial and household LEDs, the demand of LED packaging glue is higher and higher. At present, the packaging glue of epoxy resin and organic silicon resin materials occupies the main position, but epoxy resin packaging materials are easy to age, discolor and crisp; the organic silicon resin has poor corrosion resistance and low bonding strength. The polyurethane material contains polar group-NCO, so that the adhesive property to various materials is improved, and the polyurethane material has high reaction activity and can realize room temperature curing. The traditional method for preparing polyurethane contains MDI (diphenylmethane diisocyanate) and HDI (1, 6-hexamethylene diisocyanate), wherein MDI contains a benzene ring structure, has a high reaction rate with polyol, and is easy to yellow; HDI is an aliphatic structure and has excellent yellowing resistance, but has the disadvantages of unpleasant pungent odor and great harm to human body.
Disclosure of Invention
The invention provides a polyurethane preparation method based on HMDI, which utilizes the characteristics of environment friendliness, low volatility and no odor of HMDI (4, 4' -dicyclohexylmethane diisocyanate), replaces the traditional MDI and HDI to prepare polyurethane packaging adhesive, and can prepare the polyurethane packaging adhesive which is environment-friendly, non-toxic and harmless and can be cured at room temperature.
The technical scheme of the invention is as follows:
a method for preparing a polyurethane based on HMDI, comprising the steps of:
s1: according to HMDI: polyether glycol (Mn 1000): polyether glycol (Mn ═ 2000): polyether glycol (Mn ═ 3000): phenol: DOP (dioctyl phthalate) ═ 1: 0.5: 0.5: 0.05: 1: 0.01, adding polyether diol (Mn is 1000), polyether diol (Mn is 2000), polyether diol (Mn is 3000) and DOP into a three-neck flask in sequence according to the sequence of solid first and liquid second, reacting for 1.5 hours at 120 ℃ for dehydration until the water content is within 0.05%, introducing dry nitrogen for protection, adding HMDI when the temperature is reduced to 60 ℃, reacting for 2 hours at 85 ℃, finally adding phenol, stopping introducing nitrogen, preparing the curing agent prepolymer, and sealing for later use;
s2: according to the prepolymer of the curing agent: solvent: filling: pigment: leveling agent 100: 90: 115: 15: 5, adding the components into a three-neck flask, introducing dry nitrogen for protection, stirring for 1 hour at room temperature to obtain a component A, and sealing for later use;
s3: according to the curing agent: solvent: filling: pigment: deblocking accelerator 100: 70: 220: 10: 10, adding the components into a three-neck flask, introducing dry nitrogen for protection, stirring for 30min at room temperature, standing for 1 hour to obtain a component B, and sealing for later use;
s4: mixing the component A and the component B according to the weight ratio of 10: 1, stirring at room temperature to uniformly mix, and defoaming in a vacuum defoaming machine to prepare the polyurethane packaging adhesive.
The room temperature mentioned above means 25 ℃.
Further, acetone or dimethyl carbonate is used as a solvent.
Furthermore, titanium dioxide is used as the filler.
Further, phthalocyanine blue is used as the pigment.
Further, a trojan antifoaming agent (Troysol AFL) is adopted as the leveling agent.
Further, butanediol is used as a curing agent.
Furthermore, the deblocking accelerant adopts hexamethylenetetramine.
The invention has the beneficial effects that:
the HMDI structure does not contain benzene rings, has excellent yellowing resistance, is low in volatility, basically has no odor and is low in harm to human bodies, the HMDI is used as a raw material to prepare the curing agent prepolymer, and the A, B component formula is adjusted to prepare the environment-friendly, non-toxic and harmless polyurethane packaging adhesive which can be cured at room temperature.
Detailed Description
The present invention will now be described in detail by way of examples.
Example 1:
polyurethane has excellent waterproof and acid-resistant properties, good flexibility and impact resistance, and can be quickly recovered after deformation, so that the polyurethane packaging material is increasingly concerned by people. The traditional method for preparing polyurethane is characterized in that MDI and HDI are adopted, wherein MDI contains a benzene ring structure, has a faster reaction rate with polyhydric alcohol and is easy to yellow; HDI is an aliphatic structure and has excellent yellowing resistance, but has the disadvantages of unpleasant pungent odor and great harm to human body. The HMDI structure does not contain benzene rings, has excellent yellowing resistance, and is low in volatility, basically free of odor and low in harm to human bodies. The curing agent prepolymer is prepared by using HMDI as a raw material, and the A, B component formula is adjusted to prepare the environment-friendly, nontoxic and harmless polyurethane packaging adhesive which can be cured at room temperature.
The manufacturing steps of the invention are as follows:
s1: according to HMDI: polyether glycol (Mn 1000): polyether glycol (Mn ═ 2000): polyether glycol (Mn ═ 3000): phenol: DOP ═ 1: 0.5: 0.5: 0.05: 1: 0.01, adding polyether diol (Mn is 1000), polyether diol (Mn is 2000), polyether diol (Mn is 3000) and DOP into a three-neck flask in sequence according to the sequence of solid first and liquid second, reacting for 1.5 hours at 120 ℃ for dehydration until the water content is within 0.05%, introducing dry nitrogen for protection, adding HMDI when the temperature is reduced to 60 ℃, reacting for 2 hours at 85 ℃, finally adding phenol, stopping introducing nitrogen, preparing the curing agent prepolymer, and sealing for later use;
s2: according to the prepolymer of the curing agent: solvent: filling: pigment: leveling agent 100: 90: 115: 15: 5, adding the components into a three-neck flask, introducing dry nitrogen for protection, stirring for 1 hour at room temperature to obtain a component A, and sealing for later use;
s3: according to the curing agent: solvent: filling: pigment: deblocking accelerator 100: 70: 220: 10: 10, adding the components into a three-neck flask, introducing dry nitrogen for protection, stirring for 30min at room temperature, standing for 1 hour to obtain a component B, and sealing for later use;
s4: mixing the component A and the component B according to the weight ratio of 10: 1, stirring at room temperature to uniformly mix, and defoaming in a vacuum defoaming machine to prepare the polyurethane packaging adhesive.
In this embodiment, the solvent is acetone or dimethyl carbonate, the filler is titanium dioxide, the pigment is phthalocyanine blue, the leveling agent is a trojan defoamer, the curing agent is butanediol, and the deblocking promoter is hexamethylenetetramine.
The polyurethane packaging adhesive prepared by the method can be cured within 60min at room temperature.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (7)

1. A method for preparing polyurethane based on HMDI is characterized by comprising the following steps:
s1: according to HMDI: polyether glycol having Mn of 1000: polyether glycol having Mn of 2000: polyether glycol having Mn of 3000: phenol: DOP ═ 1: 0.5: 0.5: 0.05: 1: 0.01, firstly adding polyether glycol with Mn of 1000, polyether glycol with Mn of 2000, polyether glycol with Mn of 3000 and DOP into a three-neck flask in sequence of solid first and liquid second, reacting for 1.5 hours at 120 ℃ for dehydration till the water content is within 0.05 percent, then introducing dry nitrogen for protection, adding HMDI when the temperature is reduced to 60 ℃, reacting for 2 hours at 85 ℃, finally adding phenol, stopping introducing nitrogen, thus preparing a curing agent prepolymer, and sealing for later use;
s2: according to the prepolymer of the curing agent: solvent: filling: pigment: leveling agent 100: 90: 115: 15: 5, adding the components into a three-neck flask, introducing dry nitrogen for protection, stirring for 1 hour at room temperature to obtain a component A, and sealing for later use;
s3: according to the curing agent: solvent: filling: pigment: deblocking accelerator 100: 70: 220: 10: 10, adding the components into a three-neck flask, introducing dry nitrogen for protection, stirring for 30min at room temperature, standing for 1 hour to obtain a component B, and sealing for later use;
s4: mixing the component A and the component B according to the weight ratio of 10: 1, stirring at room temperature to uniformly mix, and defoaming in a vacuum defoaming machine to prepare the polyurethane packaging adhesive.
2. A HMDI-based polyurethane preparation process according to claim 1, characterized in that the solvent is acetone or dimethyl carbonate.
3. The process for the preparation of polyurethane based on HMDI as claimed in claim 1, wherein the filler is titanium dioxide.
4. A HMDI-based polyurethane preparation process according to claim 1, characterized in that the pigment is phthalocyanine blue.
5. The HMDI-based polyurethane preparation method of claim 1, wherein the leveling agent is a Trojan defoamer.
6. A HMDI-based polyurethane preparation process according to claim 1, wherein the curing agent is butanediol.
7. A process for HMDI-based polyurethane according to claim 1, wherein the deblocking promoter is hexamethylenetetramine.
CN201911378300.2A 2019-12-27 2019-12-27 HMDI-based polyurethane preparation method Pending CN111040718A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911378300.2A CN111040718A (en) 2019-12-27 2019-12-27 HMDI-based polyurethane preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911378300.2A CN111040718A (en) 2019-12-27 2019-12-27 HMDI-based polyurethane preparation method

Publications (1)

Publication Number Publication Date
CN111040718A true CN111040718A (en) 2020-04-21

Family

ID=70240704

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911378300.2A Pending CN111040718A (en) 2019-12-27 2019-12-27 HMDI-based polyurethane preparation method

Country Status (1)

Country Link
CN (1) CN111040718A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880178A (en) * 1993-07-28 1999-03-09 Elf Atochem North America, Inc. Catalyst for low temperature cure of blocked isocyanates
CN101550327A (en) * 2008-04-03 2009-10-07 航天材料及工艺研究所 High hardness high-toughness polyurethane casting compound and application thereof
CN101760166A (en) * 2009-12-22 2010-06-30 广州鹿山新材料股份有限公司 Non-yellowing thermoplastic polyurethane hot melt adhesive and preparation method thereof
CN102295906A (en) * 2010-06-24 2011-12-28 上海海鹰粘接科技有限公司 High-strength yellowing-resistant elastic polyurethane adhesive and preparation method as well as application thereof
CN104893644A (en) * 2015-06-09 2015-09-09 中国科学技术大学 Solvent type polyurethane structure adhesive and preparation method thereof
CN106928895A (en) * 2017-03-09 2017-07-07 宜兴市普利泰电子材料有限公司 Flexible LED lamp bar polyurethane electronic casting glue and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880178A (en) * 1993-07-28 1999-03-09 Elf Atochem North America, Inc. Catalyst for low temperature cure of blocked isocyanates
CN101550327A (en) * 2008-04-03 2009-10-07 航天材料及工艺研究所 High hardness high-toughness polyurethane casting compound and application thereof
CN101760166A (en) * 2009-12-22 2010-06-30 广州鹿山新材料股份有限公司 Non-yellowing thermoplastic polyurethane hot melt adhesive and preparation method thereof
CN102295906A (en) * 2010-06-24 2011-12-28 上海海鹰粘接科技有限公司 High-strength yellowing-resistant elastic polyurethane adhesive and preparation method as well as application thereof
CN104893644A (en) * 2015-06-09 2015-09-09 中国科学技术大学 Solvent type polyurethane structure adhesive and preparation method thereof
CN106928895A (en) * 2017-03-09 2017-07-07 宜兴市普利泰电子材料有限公司 Flexible LED lamp bar polyurethane electronic casting glue and preparation method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DOUGLAS A. WICKS 等: "Blocked isocyanates III: Part A. Mechanisms and chemistry", 《PROGRESS IN ORGANIC COATINGS》 *
何杰勇: "HMDI制备室温固化聚氨酯电子封装胶", 《现代盐化工》 *
宋小平 等: "《石油化学助剂及石油产品制造技术》", 31 October 2011, 科学技术文献出版社 *
朱园勤 等: "封端异氰酸酯化学", 《化学与粘合》 *
李红强 等: "《胶粘原理、技术及应用》", 31 January 2014, 华南理工大学出版社 *
杨志等: "环保型聚氨酯塑胶跑道胶粘剂的研究", 《新型建筑材料》 *

Similar Documents

Publication Publication Date Title
CN106634778B (en) Environment-friendly polyurethane adhesive and preparation method and application thereof
CN105255432B (en) A kind of polyurethane pouring sealant and preparation method thereof
CN107083229B (en) Preparation method of double-component polyurethane pouring sealant for water treatment membrane
CN101580686A (en) Low-density high-impact-resistance epoxy resin pouring sealant and preparation method thereof
CN106397780B (en) Preparation method of functional epoxy resin curing agent
CN105461877A (en) Synthetic method of thermocuring polyurethane elastomer composite material for sealing materials
CN111849410A (en) Halogen-free flame-retardant heat-conducting polyurethane pouring sealant and preparation method thereof
CN110128269A (en) A kind of vegetable oil polyol and its preparation method and application
CN105331088A (en) Pultrusion PU (polyurethane) resin composite material and preparation method thereof
TW200504107A (en) Aqueous coating agent
CN104293159A (en) Environment-friendly heat-resistant waterborne polyurethane coating
CA2251126C (en) Reactivity improvement of urethane prepolymers of allophanate-modified diphenylmethane diisocyanates
CN105131227B (en) A kind of use for synthetic leather UV cured flame-retardant polyurethane and preparation method thereof
CN101434826A (en) Preparations of bicomponent PSU type liquid rubber-based sealant and PSU liquid rubber thereof
CN104263307A (en) Room temperature curing polyurethane encapsulating material and preparation method thereof
CN105238255A (en) Oil-resistant heat-resistant modified polyurethane coating
CN112708340A (en) Anti-sagging single-component polyurethane waterproof coating capable of being sprayed and constructed
CN107987782A (en) A kind of preparation method of aspartate casting glue
CN113512173A (en) High-strength self-repairing polyurethane material and preparation method thereof
CN111117465B (en) Environment-friendly single-component polyurethane waterproof coating
CN112225872A (en) Waterborne polyurethane and preparation method thereof
CN114181605B (en) Single-component water-based polyurethane waterproof coating and preparation method thereof
CN108018017B (en) Water-based environment-friendly polyurethane adhesive, and preparation method and application thereof
CN111040718A (en) HMDI-based polyurethane preparation method
CN113429873A (en) Low-free TDI type single-component polyurethane waterproof paint and preparation method thereof

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200421