Sulfur-containing phenol formaldehyde resin and preparation method thereof

Abstract

The invention provides sulfur-containing phenol formaldehyde resin and a preparation method thereof. Resin can be subjected to a reaction by taking phenol containing different substituent groups as raw materials and also can have the different sulfur contents. The molecular structure of the sulfur-containing phenol formaldehyde resin not only contains sulfur, but also contains a structure of the phenol formaldehyde resin. Sulfur can serve as a sulphur donor to achieve the crosslinking effect (such as a sulfurization reaction) and also can react with metal substances; the phenol formaldehyde resin can achieve the effects of bonding, reinforcing, insulating, high temperature resisting, corrosion resisting and the like, and therefore the phenol formaldehyde resin can be applied to the fields of rubber, plastic, paint, adhesives, printing ink, synthetic fibers, anti-corrosive and high-temperature-resisting materials, semiconductor materials and the like. The preparation method of the sulfur-containing phenol formaldehyde resin comprises the steps that phenol or alkylphenol is utilized to react with sulphur chloride to prepare a phenol or alkylphenol sulfide monomer or oligomer, the phenol or alkylphenol sulfide monomer or oligomer reacts with phenol or alkylphenol and formaldehyde under the acidic condition, and then the sulfur-containing phenol formaldehyde resin is prepared.

Description

technical field

[0001] The invention relates to a phenolic resin and its preparation method and application, in particular to a sulfur-containing phenolic resin and its preparation method and application. Background technique

[0002] In 1872, German chemist A. Baeyer first discovered that phenol and aldehyde could be condensed in the presence of acid to obtain an amorphous brown-red intractable resinous product (Huang Farong, edited by Jiao Yangsheng. Phenolic resin and its application. Chemical Industry Press). From then on, people began to study phenolic resins, and constantly optimized the preparation process, and constantly modified phenolic resins to meet the needs of practical applications. Phenolic resins are mainly used in rubber, plastics, coatings, adhesives, inks, synthetic fibers, anti-corrosion and high-temperature resistant materials, semiconductor materials and other fields. The development and research work on phenolic resins revolves around reinforcement,...

Examples

preparation example Construction

[0046] 1. Preparation of sulfur-containing phenolic resin

[0047] 1.1 Raw materials and reagents

[0048] Table 1

[0049] raw material name

source

phenol

Sinopharm Group

cresol

Sinopharm Group

Styrenated phenol

Sinopharm Group

PTBP

Sinopharm Group

PTOP

Sinopharm Group

Sulfur monochloride (S 2 Cl 2 )

Sinopharm Group

[0050] 1.2 Instruments and equipment

[0051] Table 2

[0052] model and name

manufacturer

CS-580 Elemental Analyzer

Elter, Germany

Agilent 7890A Gas Chromatograph

AGILENT TECHNOLOGIES

FP900 calorific value analyzer

METTLER TOLEDO

[0053] 1.3 Analysis and Testing

[0054] (1) Free phenol content test: test the free phenol content of the product according to ISO8974-2002.

[0055] (2) Sulfur content test: test the sulfur content according to GBT4497.1-2010.

[0056] (3) Softening point test: test the softening poi...

Embodiment 1

[0058] Embodiment 1, the preparation of phenol disulfide

[0059]

[0060] Add 56.5g of 0.6mol phenol liquid and 17.0g of toluene to a 250mL four-necked flask equipped with a temperature control device, a stirring device and a distillation device. The air in the reactor was replaced by nitrogen gas, and the temperature was controlled at 80°C. Slowly add 40.5g0.3molS dropwise within 2h under the protection of nitrogen 2 Cl 2 liquid. The tail gas of the distillation unit is passed into 10% sodium hydroxide solution to neutralize the hydrogen chloride gas produced by the reaction. S 2 Cl 2 After the liquid was added dropwise, the mixture was stirred and reacted at 90° C. for 2 h under the protection of nitrogen. In the state of distillation, the reaction temperature was raised for distillation, and when the temperature rose to 120°C, the distillation was carried out under reduced pressure for 30 minutes, and the product A phenol disulfide was finally obtained as a browni...

Embodiment 2-8

[0061] The preparation of embodiment 2-8, alkylphenol disulfide

[0062] Repeat the steps of Example 1, change the phenol in the reaction raw material into cresol (MP), p-tert-butylphenol (PTBP), p-tert-octylphenol (PTOP), styrenated phenol (SP), or the above alkyl A mixture of phenols. Change the S in the reaction raw material 2 Cl 2 The amount of liquid, based on the amount of alkylphenol, use 50%-60% S 2 Cl 2 Liquid experiments were performed to prepare Product A alkylphenol disulfide monomers or oligomers. Select toluene as reaction solvent, take alkylphenol as the basis of weight, use 20%-30% toluene to carry out experiments, solvent toluene is added in the reactor together with reaction raw material alkylphenol, other feed intake and its reaction conditions are constant, The obtained product is as follows, and the specific raw material consumption and product index are shown in Table 3.

[0063]

[0064] table 3

[0065]

[0066] Note: Examples 6, 7, and 8 a...

technical field

[0001] The invention relates to a phenolic resin and its preparation method and application, in particular to a sulfur-containing phenolic resin and its preparation method and application. Background technique

[0002] In 1872, German chemist A. Baeyer first discovered that phenol and aldehyde could be condensed in the presence of acid to obtain an amorphous brown-red intractable resinous product (Huang Farong, edited by Jiao Yangsheng. Phenolic resin and its application. Chemical Industry Press). From then on, people began to study phenolic resins, and constantly optimized the preparation process, and constantly modified phenolic resins to meet the needs of practical applications. Phenolic resins are mainly used in rubber, plastics, coatings, adhesives, inks, synthetic fibers, anti-corrosion and high-temperature resistant materials, semiconductor materials and other fields. The development and research work on phenolic resins revolves around reinforcement,...

Examples

preparation example Construction

[0046] 1. Preparation of sulfur-containing phenolic resin

[0047] 1.1 Raw materials and reagents

[0048] Table 1

[0049] raw material name

source

phenol

Sinopharm Group

cresol

Sinopharm Group

Styrenated phenol

Sinopharm Group

PTBP

Sinopharm Group

PTOP

Sinopharm Group

Sulfur monochloride (S 2 Cl 2 )

Sinopharm Group

[0050] 1.2 Instruments and equipment

[0051] Table 2

[0052] model and name

manufacturer

CS-580 Elemental Analyzer

Elter, Germany

Agilent 7890A Gas Chromatograph

AGILENT TECHNOLOGIES

FP900 calorific value analyzer

METTLER TOLEDO

[0053] 1.3 Analysis and Testing

[0054] (1) Free phenol content test: test the free phenol content of the product according to ISO8974-2002.

[0055] (2) Sulfur content test: test the sulfur content according to GBT4497.1-2010.

[0056] (3) Softening point test: test the softening poi...

Embodiment 1

[0058] Embodiment 1, the preparation of phenol disulfide

[0059]

[0060] Add 56.5g of 0.6mol phenol liquid and 17.0g of toluene to a 250mL four-necked flask equipped with a temperature control device, a stirring device and a distillation device. The air in the reactor was replaced by nitrogen gas, and the temperature was controlled at 80°C. Slowly add 40.5g0.3molS dropwise within 2h under the protection of nitrogen 2 Cl 2 liquid. The tail gas of the distillation unit is passed into 10% sodium hydroxide solution to neutralize the hydrogen chloride gas produced by the reaction. S 2 Cl 2 After the liquid was added dropwise, the mixture was stirred and reacted at 90° C. for 2 h under the protection of nitrogen. In the state of distillation, the reaction temperature was raised for distillation, and when the temperature rose to 120°C, the distillation was carried out under reduced pressure for 30 minutes, and the product A phenol disulfide was finally obtained as a browni...

Embodiment 2-8

[0061] The preparation of embodiment 2-8, alkylphenol disulfide

[0062] Repeat the steps of Example 1, change the phenol in the reaction raw material into cresol (MP), p-tert-butylphenol (PTBP), p-tert-octylphenol (PTOP), styrenated phenol (SP), or the above alkyl A mixture of phenols. Change the S in the reaction raw material 2 Cl 2 The amount of liquid, based on the amount of alkylphenol, use 50%-60% S 2 Cl 2 Liquid experiments were performed to prepare Product A alkylphenol disulfide monomers or oligomers. Select toluene as reaction solvent, take alkylphenol as the basis of weight, use 20%-30% toluene to carry out experiments, solvent toluene is added in the reactor together with reaction raw material alkylphenol, other feed intake and its reaction conditions are constant, The obtained product is as follows, and the specific raw material consumption and product index are shown in Table 3.

[0063]

[0064] table 3

[0065]

[0066] Note: Examples 6, 7, and 8 a...

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