CN112645856A - Preparation method of viscosity-controllable polythiol - Google Patents

Preparation method of viscosity-controllable polythiol Download PDF

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CN112645856A
CN112645856A CN202011513911.6A CN202011513911A CN112645856A CN 112645856 A CN112645856 A CN 112645856A CN 202011513911 A CN202011513911 A CN 202011513911A CN 112645856 A CN112645856 A CN 112645856A
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polythiol
epoxidation
reaction
thioetherification
viscosity
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CN112645856B (en
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马雪菲
梁万根
崔卫华
费潇瑶
宋吻吻
王胜飞
卞文
杨后奇
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Shandong Efirm Biochemistry and Environmental Protection Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The invention belongs to the field of chemical industry, and particularly relates to a preparation method of viscosity-controllable polythiol. The method comprises the steps of firstly reacting polyether polyol with epoxy chloropropane, then removing HCl for epoxidation under an alkaline condition, and then carrying out sulfhydrylation with hydrogen sulfide, so that the content of sulfhydryls can be accurately controlled.

Description

Preparation method of viscosity-controllable polythiol
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a preparation method of viscosity-controllable polythiol.
Background
The epoxy adhesive has the advantages of low volatile matter during curing, small shrinkage, high bonding strength, good toughness, good solvent resistance, good water resistance, environmental aging resistance, excellent electrochemical performance and the like, and plays an important role in synthesizing the adhesive. The epoxy resin curing agent can be used as building structural adhesive, electronic packaging adhesive and the like with excellent performance after crosslinking reaction. Common polyamine and anhydride curing agents are difficult to cure at low temperature, and the service time and the application field of the curing agents are limited.
The polythiol curing agent is used as a novel epoxy resin curing agent, has a plurality of high-activity group sulfydryl on the terminal group, can be crosslinked and cured with epoxy resin, and has the advantages of low curing temperature, rapid curing, excellent performance after curing and the like.
The polythiol curing agent generally adopts a synthetic process of ring-opening substitution of polyether polyol and epoxy chloropropane and sulfhydrylation of the polyether polyol and sodium hydrosulfide, the process has single product production, different production processes need to be developed for polythiol products with different viscosities and sulfhydryl contents, and the conditions are complex.
Disclosure of Invention
In order to solve the problems of the prior art, the preparation method of the viscosity-controllable polythiol comprises the steps of firstly reacting polyether polyol with epoxy chloropropane, then removing HCl and epoxidizing under an alkaline condition, and then carrying out sulfhydrylation with hydrogen sulfide, wherein the sulfydryl content can be accurately controlled.
The invention provides a preparation method of viscosity-controllable polythiol, which comprises the following steps:
a) reacting low molecular weight polyether with epoxy chloropropane (EPCH) under the catalysis of Lewis acid at 130-160 ℃ to generate a chlorine-containing polyether intermediate (PCE), wherein the specific reaction formula is as follows:
Figure BDA0002841346180000011
wherein R is
Figure BDA0002841346180000012
N is 0 to 5, and x is 2 to 4.
The mass ratio of the EPCH to the low molecular weight polyether is (2-4): 1;
the lewis acid catalyst includes: AlCl3、BF2、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2One kind of (1). The reaction time is 2-4 h;
b) adding the PCE and the NaHS into a four-neck flask according to a ratio, synthesizing a thioetherification intermediate at the temperature of 60-70 ℃ for 1-2 h, and washing and refining the thioetherification intermediate for later use;
in the reaction process of the step, two-CH in the chlorine-containing polyether intermediate obtained in the step a) are2Cl reacts with NaHS to obtain-CH2─S─CH2The structure of (a), wherein the PCE to NaHS ratio determines how much of the structure and the size and structure of the thioetherification intermediate. Therefore, the proportion of the PCE to the NaHS is directly related to the viscosity of the final product, the proportion of the PCE to the NaHS can be adjusted according to production requirements, the molar ratio of the PCE to the NaHS is within the range of 1: 0.1-2, and products with different performances and with the product viscosity (25 ℃) of 2000-20000 mpa.s can be obtained.
c) Removing HCl from the refined thioetherification intermediate under an alkaline condition, performing epoxidation, washing with water, and refining to obtain an epoxidation intermediate;
preferably, the alkaline condition can be realized by adding an alkaline component, wherein the alkaline component is selected from one or more of sodium ethoxide, sodium methoxide, NaOH and KOH;
wherein the addition amount of the alkaline component accounts for 3-10% of the mass ratio of the thioetherification intermediate, the epoxidation temperature is 25-40 ℃, and the epoxidation time is 5-10 h.
d) Epoxidation of intermediates in hydrogen sulfide (H)2S) carrying out high-pressure ring-opening sulfhydrylation reaction in a gas environment, and washing and refining the product to obtain a high-quality polythiol product.
The reaction pressure is 0.4-1.2 MPa, the reaction temperature is 50-130 ℃, and the sulfhydrylation time is 4-6 h.
The preparation method of the viscosity-controllable polythiol can flexibly control the content of the terminal sulfydryl of the polythiol, the molecular weight of the polythiol and the viscosity range, and meet different applications and customer requirements. Test results prove that the polythiol prepared by the method can accurately control the position of sulfydryl, avoids the defect that side reactions are uncontrollable in the sulfhydrylation process of sodium hydrosulfide, thiourea and the like, and has stable product performance and strong controllability in the reaction process.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention. Except as otherwise noted, the following examples were carried out using conventional techniques.
Example 1
a) Low molecular weight polyethers
Figure BDA0002841346180000022
And the reaction product is subjected to addition reaction with epoxy chloropropane (EPCH) under the catalysis of Lewis acid at 140 ℃ to generate a chlorine-containing polyether intermediate (PCE), and the specific reaction formula is as follows:
wherein R is
Figure BDA0002841346180000021
n is 3 and x is 2.
The mass ratio of the EPCH to the low molecular weight polyether is 2: 1;
the Lewis acid catalyst is AlCl3The reaction time is 2 h;
b) the PCE and the NaHS are added into a four-neck flask according to a certain proportion, a thioetherification intermediate is synthesized for 2 hours at the temperature of 60 ℃, and the thioetherification intermediate is washed by water and refined for later use;
the molar ratio of PCE to NaHS was chosen to be 1: 0.5.
c) Removing HCl from the refined thioetherification intermediate under an alkaline condition for epoxidation, washing with water, and refining to obtain an epoxidation intermediate; the basic component sodium methoxide;
wherein the addition amount of sodium methoxide accounts for 10% of the mass ratio of the thioetherification intermediate, the epoxidation temperature is 40 ℃, and the epoxidation time is 5 h.
d) Epoxidation of intermediates in hydrogen sulfide (H)2S) carrying out high-pressure ring-opening sulfhydrylation reaction in a gas environment, and washing and refining the product to obtain a high-quality polythiol product.
The reaction pressure is 1.2MPa, the reaction temperature is 100 ℃, and the sulfhydrylation time is 4 h.
Example 2
a) The method comprises the following steps of carrying out addition reaction on low molecular weight polyether and epoxy chloropropane (EPCH) under the catalysis of Lewis acid at 130-160 ℃ to generate a chlorine-containing polyether intermediate (PCE), wherein the specific reaction formula is as follows:
wherein R is
Figure BDA0002841346180000031
n is 5 and x is 3.
The mass ratio of the EPCH to the low molecular weight polyether is 3: 1;
the Lewis acid catalyst is FeBr3(ii) a The reaction time is 3 h;
b) the PCE and the NaHS are added into a four-neck flask according to a certain proportion, a thioetherification intermediate is synthesized for 1h at the temperature of 70 ℃, and is washed by water and refined for later use;
the molar ratio of PCE to NaHS was chosen to be 1: 1.
c) Removing HCL from the refined thioetherification intermediate under an alkaline condition for epoxidation, washing with water, and refining to obtain an epoxidation intermediate;
the alkaline component NaOH;
wherein the addition amount of the alkaline component accounts for 3% of the mass ratio of the thioetherification intermediate, the epoxidation temperature is 25 ℃, and the epoxidation time is 10 hours.
d) Epoxidation of intermediates in hydrogen sulfide (H)2S) carrying out high-pressure ring-opening sulfhydrylation reaction in a gas environment, and washing and refining the product to obtain a high-quality polythiol product.
The reaction pressure is 0.6MPa, the reaction temperature is 130 ℃, and the sulfhydrylation time is 5 h.
Example 3
a) The method comprises the following steps of carrying out addition reaction on low molecular weight polyether and epoxy chloropropane (EPCH) under the catalysis of Lewis acid at 130-160 ℃ to generate a chlorine-containing polyether intermediate (PCE), wherein the specific reaction formula is as follows:
wherein R is
Figure BDA0002841346180000032
n is 4 and x is 4.
The mass ratio of the EPCH to the low molecular weight polyether is 4: 1;
the Lewis acid catalyst is SnCl4. The reaction time is 4 h;
b) the PCE and the NaHS are added into a four-neck flask according to a certain proportion, a thioetherification intermediate is synthesized for 1.5h at the temperature of 65 ℃, and the thioetherification intermediate is washed by water and refined for later use;
the molar ratio of PCE to NaHS was chosen to be 1: 2.
c) Removing HCl from the refined thioetherification intermediate under an alkaline condition for epoxidation, washing with water, and refining to obtain an epoxidation intermediate;
the alkaline component is KOH;
wherein the addition amount of the alkaline component accounts for 6% of the mass ratio of the thioetherification intermediate, the epoxidation temperature is 30 ℃, and the epoxidation time is 7 h.
d) Epoxidation of intermediates in hydrogen sulfide (H)2S) carrying out high-pressure ring-opening sulfhydrylation reaction in a gas environment, and washing and refining the product to obtain a high-quality polythiol product.
The reaction pressure is 1MPa, the reaction temperature is 120 ℃, and the sulfhydrylation time is 5 hours.
The final polythiol product in each of the above examples was tested for performance and verified for curing performance:
polythiol product properties:
example 1 Example 2 Example 3
Content of mercapto group/%) 18.7 12.5 10.7
chroma/Hazen 9 9.7 10.3
Viscosity (25 ℃ C.)/mpa.s 5420 12500 19500
Chlorine residue/ppm 207 185 151
And (3) verifying the curing performance:
the polythiols obtained in examples 1 to 3 were reacted with epoxy resins E54, E51, E44 in terms of the mercapto content: the adhesive is compounded according to the proportion of 1:1 of epoxy equivalent, 10% of polythiol by mass and 2, 4, 6-tris (dimethylaminomethyl) phenol (DMP-30) as an accelerator are added, and the gel time of different formulas is tested, and the specific results are shown below.
Polythiols Example 1 Example 2 Example 3
Epoxy resin E54:E51＝2:1 E51 E51:E44＝1:1
Accelerator DMP-30 DMP-30 DMP-30
Gel time/min 6.5 4.2 2.4
The polythiol product has adjustable viscosity and sulfydryl content as required, meets different scenes, is tried in different epoxy resin systems, and has short gelling time and quick curing.

Claims (7)

1. A method for preparing a viscosity-controlled polythiol, comprising the steps of:
a) reacting low molecular weight polyether with epoxy chloropropane EPCH under the catalysis of Lewis acid at 130-160 ℃ to generate a chlorine-containing polyether intermediate PCE, wherein the specific reaction route is as follows:
Figure FDA0002841346170000011
wherein R is
Figure FDA0002841346170000012
N is 0-5, x is 2-4;
b) adding the PCE and the NaHS into a four-neck flask according to a ratio, synthesizing a thioetherification intermediate at the temperature of 60-70 ℃ for 1-2 h, and washing and refining the thioetherification intermediate for later use;
c) removing HCl from the refined thioetherification intermediate under an alkaline condition, performing epoxidation, washing with water, and refining to obtain an epoxidation intermediate;
d) and (3) carrying out high-pressure ring-opening sulfhydrylation reaction on the epoxidation intermediate in a hydrogen sulfide gas environment, and washing and refining the product to obtain a polythiol product.
2. The method of claim 1, wherein the mass ratio of the EPCH to the low molecular weight polyether in step a) is 2-4: 1, the reaction time is 2-4 h.
3. The method of claim 1, wherein the lewis acid catalyst comprises: AlCl3、BF2、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2One kind of (1).
4. The method for preparing a viscosity-controllable polythiol according to claim 1, wherein the molar ratio of PCE to NaHS in step b) is in the range of 1: 0.1-2, and the viscosity of the obtained polythiol is 2000-20000 mpa.s at 25 ℃.
5. The method of claim 1, wherein the alkaline condition in step c) is achieved by adding an alkaline component selected from one or more of quaternary ammonium compounds, sodium ethoxide, sodium methoxide, NaOH, and KOH.
6. The method according to claim 5, wherein the alkaline component is added in an amount of 3-10% by mass of the thioetherification intermediate, the epoxidation temperature is 25-40 ℃, and the epoxidation time is 5-10 hours.
7. The method of claim 1, wherein the reaction pressure in step d) is 0.8-1.2 MPa, the reaction temperature is 100-130 ℃, and the sulfhydrylation time is 4-6 h.
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Cited By (3)

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CN113956444A (en) * 2021-11-10 2022-01-21 广州飞思合成材料有限公司 Epoxy curing agent and preparation method thereof
CN115873225A (en) * 2022-12-29 2023-03-31 广州市白云化工实业有限公司 Polyester epoxy diluent, epoxy adhesive and preparation method thereof
CN117343477A (en) * 2023-09-28 2024-01-05 益丰新材料股份有限公司 Curable composition and application thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956444A (en) * 2021-11-10 2022-01-21 广州飞思合成材料有限公司 Epoxy curing agent and preparation method thereof
CN113956444B (en) * 2021-11-10 2023-09-22 广州飞思合成材料有限公司 Epoxy curing agent and preparation method thereof
CN115873225A (en) * 2022-12-29 2023-03-31 广州市白云化工实业有限公司 Polyester epoxy diluent, epoxy adhesive and preparation method thereof
CN117343477A (en) * 2023-09-28 2024-01-05 益丰新材料股份有限公司 Curable composition and application thereof

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