CN102516891B - Single-component anaerobic adhesive with high filing gap and preparation method thereof - Google Patents

Abstract

The invention relates to a single-component anaerobic adhesive with high filing gap and a preparation method thereof, and belongs to the technical field of anaerobic adhesives. Due to the great influence of gap on the curing of a present anaerobic adhesive, its curing effect is very poor when the gap exceeds 0.5mm and even the present anaerobic adhesive can not be cured. The above problem of the present anaerobic adhesive is solved in the invention. The anaerobic adhesive provided by the invention is mainly characterized by comprising: (A) 50-98 wt% of a terminated unsaturated monomer containing at least one vinyl with the molecular weight being less than 600; (B) 0-30 wt% of a plasticizer; (C) 0-20 wt% of a powder; (D) 0.02-1 wt% of a polymerization inhibitor; (E) 1-3 wt% of N-acetylphenylhydrazine; (F) 0.5-5 wt% of benzoyl sulfonic imide; (G) 0.01-0.1% of a metal ion chelating agent; (H) 0.1-5% of a peroxide initiator; and (I) 0-20% of fumed silica. The filling gap in the invention can reach more than 5mm. The anaerobic adhesive has excellent storage stability. Failure moment and average dismounting moment can be adjusted within 0.1-30N.m. sealing performance can reach 1MPa (air pressure) without leakage. Static shearing strength can reach more than 25 MPa. The invention mainly provides the single-component anaerobic adhesive with high filing gap and the preparation method thereof.

Description

A kind of single-component anaerobic adhesive with high filing gap and preparation method thereof

Technical field

The invention belongs to the anaerobic glue technical field, be specifically related to a kind of single-component anaerobic adhesive with high filing gap, anaerobically curable, be widely used in thread locking, pipe thread seal, flat seal, the part fixing of the industries such as automobile, engineering machinery, electronic apparatus.

Background technology

As everyone knows, the curing of anaerobic glue is subject to the impact in gap very large, if generally speaking gap surpasses 0.5mm, the solidification effect of anaerobic glue, by very poor, can't solidify even at all, and also this shortcoming makes the application of anaerobic glue be limited by very large just.Coarse thread bolt as larger as diameter or gas thread use anaerobic glue to be locked or while sealing, its effect is often poor, can only use other fastening means to carry out locking; Some flange, head side cause gap to surpass 1mm with deep trouth, and the anaerobism flat sealant can't solidify, and can't form sealing effectively, have to select rubber sheet gasket; Although sometimes also can improve this problem by the primary coat of spary anaerobic glue promotor, use primary coat both to increase operation, also increased cost, can't embody the advantage of anaerobic glue.

In sum, develop a kind of single-component anaerobic adhesive with high filing gap very necessary.

Summary of the invention

The purpose the present invention relates to is exactly a kind of single-component anaerobic adhesive with high filing gap proposed for anaerobic glue weak point set forth above.

Further purpose of the present invention is to provide a kind of method for preparing above-mentioned single-component anaerobic adhesive with high filing gap.

The technical solution of single-component anaerobic structure glue of the present invention is: a kind of single-component anaerobic adhesive with high filing gap is characterized in that: its composition comprises:

(A) unsaturated monomer that at least contains 1 ethenyl blocking that 50 ~ 98%Wt molecular weight is less than 600, it is that molecular weight is less than 600 mono acrylic ester monomer, molecular weight and is less than 600 monomethacrylates monomer, molecular weight and is less than polyurethane oligomer or its mixture that 600 dimethacrylate monomer, molecular weight are less than 600 methacrylate monomer end-blocking that described molecular weight is less than 600 the unsaturated monomer that at least contains 1 ethenyl blocking;

(B) 0 ~ 30%Wt softening agent, described softening agent is Viscotrol C, oleic acid, bialkyl ortho phthalate, phenyl alkylsulfonate, paraffin, polyoxyethylene glycol 2-ethylhexoate, polyethylene glycol (PEG) oleate, polyoxyethylene glycol lauryl, adipate polyester or its mixture;

(C) 0 ~ 20% Wt powder, described powder is polyethylene powder, polypropylene powder, polyvinyl chloride powder, polytetrafluoroethylene powder, polyvinyl butyral powder, castor oil derivative, polyacrylamide powder, Paris white, mica powder, diatomite, organobentonite, titanium dioxide or its mixture;

(D) 0.02% ~ 1%Wt stopper;

(E) 1 ~ 3%Wt N-pyrodin;

(F) 0.5 ~ 5%Wt benzoic sulfimide;

(G) 0.01% ~ 0.1% metal ion chelation agent;

(H) 0.1 ~ 5% peroxide initiator;

(I) 0 ~ 20% aerosil.

In the technology of the present invention solution, said N-pyrodin and benzoic sulfimide are promotor, the two must just likely can reach high purpose of filling gap with described ratio coupling, use separately any one all not reach this purpose, being replaced with other promotor also not necessarily has this effect.

In the technology of the present invention solution, said stopper is 1,4-naphthoquinone, Resorcinol, MEHQ or its mixture.

In the technology of the present invention solution, said metal ion chelation agent is EDTA and EDETATE SODIUM salt or its mixture.

In the technology of the present invention solution, said peroxide initiator is organic hydroperoxide class, peroxidation ketone, dialkyl peroxide class, peracid ester class and acyl peroxide.

The said method for preparing single-component anaerobic adhesive with high filing gap in the technology of the present invention solution is characterized in that comprising the following steps:

1) (A) 50 ~ 98%Wt molecular weight is less than to the unsaturated monomer that at least contains 1 ethenyl blocking, (B) 0 ~ 30%Wt softening agent, (D) 0.02% ~ 1%Wt stopper, (E) 1 ~ 3%Wt N-pyrodin, (F) benzoic sulfimide of 600 and adds respectively the glue container, stir 30mim ~ 90min under 5 ℃～35 ℃, be uniformly dissolved fully to solid materials;

2) add (C) 0 ~ 20% Wt powder, (G) 0.01% ~ 0.1% metal ion chelation agent in the glue container, under 5 ℃～35 ℃, stir 30mim ~ 90min, even to powder lot dispersing;

3) add (H) 0.1 ~ 5% peroxide initiator, (I) 0 ~ 20% aerosil in the glue container, stir 20mim ~ 30min under 5 ℃～35 ℃, to being uniformly dispersed;

4) if the more vacuum-pumping 5min of bubble except the middle bubble that removes photoresist, vacuum pressure is controlled at-0.09 ~-0.07MPa between;

5) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

The single-component anaerobic adhesive with high filing gap that adopts the inventive method to prepare is a kind of viscous liquid or paste, be stored in dark vinyon bottle (pipe), this anaerobic structure glue does not need allotment before using, versatility is good, can be used for thread locking, pipe thread seal, flat seal and part fixing etc. in the industry product assembling process such as automobile, electrical equipment, machinery.

Single-component anaerobic adhesive with high filing gap of the present invention, wherein in preparation technology, the first step churning time is controlled at 30～60min, after stirring, can carry out the second step operation, and temperature is controlled at 5 ℃～25 ℃.After stirring, discharging, glue is kept in dark vinyon bottle (pipe) stand-by.

Single-component anaerobic adhesive with high filing gap of the present invention, under room temperature condition, be in a liquid state or paste, just admittedly the time is in the 10min left and right, fills more than gap can reach 5mm package stability excellent (80 ℃ * 2h is gel not), under normal temperature, in dark vinyon bottle (pipe), can preserve more than 2 years, wracking moment and average dismounting force moment can be adjusted at 0.1 ~ 30N.m respectively as required, and sealing property can reach 1MPa(air pressure) air tight, more than quiet shearing resistance can reach 25 MPa.

The present invention mainly is to provide a kind of single-component anaerobic adhesive with high filing gap and preparation method thereof.

The accompanying drawing explanation

Fig. 1 is that the present invention fills clearance test instrument schematic diagram.

Embodiment

The following example and comparative example will be introduced the present invention more in detail, but the present invention is not limited to this.

Embodiment 1:

Proportioning

Macrogol 200 dimethacrylate (molecular weight 336) 96.26%Wt

1,4-naphthoquinone 0.02%Wt

N-pyrodin 1.7%Wt

Benzoic sulfimide 0.5%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.5%Wt

The preparation method:

1) add polyoxyethylene glycol 200 dimethacrylates, 1,4-naphthoquinone, N-pyrodin, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add the EDTA tetra-na salt, stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test:

1, stability: single-component anaerobic structure glue is put into to 80 ℃ of baking ovens and heat, measure the time that gel occurs.

2, curing speed: test according to HB5325-85.

3, wracking moment and average dismounting force moment: according to GB/T 18747.1-2002, test.

4, quiet shearing resistance: test according to HB5314-85.

5, thread seal performance: test according to HB5315-85.

6, viscosity: test according to GB/T 2794-1995.

7, fill gap d: use carbon steel sheet 2,3 to press the wedge shape of preparation shown in Fig. 1 testing tool, other sides seal with plastic plate, anaerobic glue is filled between the anaerobic glue fill area to 1 from a side, the maximum cured thickness of test anaerobic glue after standing 24h, be the maximum gap d max that fills.

Test result is in Table 1.

Embodiment 2:

Proportioning:

Poly(oxyethylene glycol) 400 dimethacrylate (molecular weight 536) 91.43%Wt

1,4-naphthoquinone 0.05%Wt

N-pyrodin 1.50%Wt

Benzoic sulfimide 3.00%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 2.00%Wt

Aerosil 2.00%Wt

The preparation method:

1) add polyoxyethylene glycol 400 dimethacrylates, 1,4-naphthoquinone, N-pyrodin, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add the EDTA tetra-na salt, stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide, aerosil to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Embodiment 3:

Proportioning:

Triethylene glycol dimethacrylate (molecular weight 286) 80.45%Wt

Hydroxyethyl methylacrylate 15%Wt

1,4-naphthoquinone 0.03%Wt

N-pyrodin 1.00%Wt

Benzoic sulfimide 2.00%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.50%Wt

The preparation method:

1) add Triethylene glycol dimethacrylate, hydroxyethyl methylacrylate, 1,4-naphthoquinone, N-pyrodin, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add the EDTA tetra-na salt, stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Embodiment 4:

Proportioning:

Macrogol 200 dimethacrylate (molecular weight 336) 82.45%Wt

Polytetrafluoroethylene powder 4.00%Wt

Polyvinyl butyral acetal 4.00%Wt

1,4-naphthoquinone 0.03%Wt

N-pyrodin 1.00%Wt

Benzoic sulfimide 3.00%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.50%Wt

Aerosil 4.00%Wt

The preparation method:

1) add Triethylene glycol dimethacrylate, hydroxyethyl methylacrylate, 1,4-naphthoquinone, N-pyrodin, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add EDTA tetra-na salt, polytetrafluoroethylene powder, polyvinyl butyral acetal, stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide, aerosil to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) vacuumize the 5min deaeration, vacuum pressure is controlled at-0.09 ~-0.07MPa between;

5) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Embodiment 5:

Proportioning:

Hydroxyethyl methylacrylate (molecular weight 130) 77.25%Wt

Polyethylene powder 10.00%Wt

1,4-naphthoquinone 0.03%Wt

N-pyrodin 1.70%Wt

Benzoic sulfimide 1.00%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.50%Wt

Aerosil 7.00%Wt

The preparation method:

1) methylate Hydroxyethyl acrylate, 1,4-naphthoquinone, N-pyrodin, benzoic sulfimide in container stir 30mim ~ 90min under 5 ℃～35 ℃, are uniformly dissolved fully to solid materials;

2) add EDTA tetra-na salt, polyethylene powder, stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide, aerosil to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Embodiment 6:

Proportioning:

Macrogol 200 dimethacrylate (molecular weight 336) 50.00%Wt

The two 2-ethylhexoate 25.65%Wt of Macrogol 200

Polyethylene powder 8.50%Wt

Polyvinyl butyral acetal 6.20%Wt

1,4-naphthoquinone 0.03%Wt

N-pyrodin 1.20%Wt

Benzoic sulfimide 2.80%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 2.00%Wt

Aerosil 3.60%Wt

The preparation method:

1) add the two 2-ethylhexoates of Triethylene glycol dimethacrylate, Macrogol 200,1,4-naphthoquinone, N-pyrodin, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add EDTA tetra-na salt, polyethylene powder, polyvinyl butyral acetal, stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide, aerosil to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) vacuumize the 5min deaeration, vacuum pressure is controlled at-0.09 ~-0.07MPa between;

5) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Comparative example 1

Proportioning

Macrogol 200 dimethacrylate 94.46%Wt

1,4-naphthoquinone 0.02%Wt

Benzoic sulfimide 4.00%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.50%Wt

The preparation method:

1) add polyoxyethylene glycol 200 dimethacrylates, 1,4-naphthoquinone, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add the EDTA tetra-na salt, stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Comparative example 2

Proportioning

Macrogol 200 dimethacrylate 94.46%Wt

1,4-naphthoquinone 0.02%Wt

Benzoic sulfimide 4.00%Wt

N, N-dimethyl Ortho Toluidine 1.00%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.50%Wt

The preparation method:

1) add polyoxyethylene glycol 200 dimethacrylates, 1,4-naphthoquinone, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add EDTA tetra-na salt, N, N-dimethyl Ortho Toluidine stirs 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Comparative example 3

Proportioning:

Ethoxyquin (10) bisphenol a dimethacrylate (molecular weight 804) 85.56%Wt

Polyethylene powder 3.50%Wt

Polyvinyl butyral acetal 4.20%Wt

1,4-naphthoquinone 0.03%Wt

N-pyrodin 1.20%Wt

Benzoic sulfimide 0.80%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.00%Wt

Aerosil 3.60%Wt

The preparation method:

1) add ethoxyquin (10) bisphenol a dimethacrylate, 1,4-naphthoquinone, benzoic sulfimide in container, under 5 ℃～35 ℃, stir 30mim ~ 90min, be uniformly dissolved fully to solid materials;

2) add EDTA tetra-na salt, polyethylene powder, polyvinyl butyral acetal to stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide, aerosil to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) vacuumize the 5min deaeration, vacuum pressure is controlled at-0.09 ~-0.07MPa between;

5) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Test result is in Table 1.

Comparative example 4

Proportioning:

The polyurethane oligomer of methacrylate monomer end-blocking (molecular weight approximately 4000) 96.25%Wt

1,4-naphthoquinone 0.03%Wt

N-pyrodin 1.20%Wt

Benzoic sulfimide 1.50%Wt

EDTA tetra-na salt 0.02%Wt

Isopropyl benzene hydroperoxide 1.00%Wt

The preparation method:

1) polyurethane oligomer, 1,4-naphthoquinone, the benzoic sulfimide of methylate acrylate monomer end-blocking in container stir 30mim ~ 90min under 5 ℃～35 ℃, are uniformly dissolved fully to solid materials;

2) add EDTA tetra-na salt, polyethylene powder, polyvinyl butyral acetal to stir 30mim ~ 90min to even under 5 ℃～35 ℃;

3) add isopropyl benzene hydroperoxide, aerosil to stir 20mim ~ 30min to even under 5 ℃～35 ℃;

4) vacuumize the 5min deaeration, vacuum pressure is controlled at-0.09 ~-0.07MPa between;

5) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

Performance test is with embodiment 1.

Claims (2)

1. a single-component anaerobic adhesive with high filing gap is characterized in that its composition comprises:

(A) 50 ~ 98%Wt unsaturated monomer, described unsaturated monomer is mixture or the hydroxyethyl methylacrylate that molecular weight is less than 600 Macrogol 200 dimethacrylate, poly(oxyethylene glycol) 400 dimethacrylate, Triethylene glycol dimethacrylate and hydroxyethyl methylacrylate;

(B) 0 ~ 30%Wt softening agent, described softening agent is Viscotrol C, oleic acid, bialkyl ortho phthalate, phenyl alkylsulfonate, paraffin, polyoxyethylene glycol 2-ethylhexoate, polyethylene glycol (PEG) oleate, polyoxyethylene glycol lauryl, adipate polyester or its mixture;

(C) 0 ~ 20% Wt powder, described powder is polyethylene powder, polypropylene powder, polyvinyl chloride powder, polytetrafluoroethylene powder, polyvinyl butyral powder, castor oil derivative, polyacrylamide powder, Paris white, mica powder, diatomite, organobentonite, titanium dioxide or its mixture;

(D) 0.02% ~ 1%Wt stopper, described stopper is 1,4-naphthoquinone, Resorcinol, MEHQ or its mixture;

(E) 1 ~ 3%Wt N-pyrodin;

(F) 0.5 ~ 5%Wt benzoic sulfimide;

(G) 0.01% ~ 0.1% metal ion chelation agent, described metal ion chelation agent is EDTA and EDETATE SODIUM salt or its mixture;

(H) 0.1 ~ 5% peroxide initiator, described peroxide initiator is organic hydroperoxide class, peroxidation ketone, dialkyl peroxide class, peracid ester class and acyl peroxide;

(I) 0 ~ 20% aerosil.

2. a preparation method who prepares single-component anaerobic adhesive with high filing gap claimed in claim 1 is characterized in that comprising the following steps:

1) (A) 50 ~ 98%Wt molecular weight is less than to unsaturated monomer, (B) 0 ~ 30%Wt softening agent, (D) 0.02% ~ 1%Wt stopper, (E) 1 ~ 3%Wt N-pyrodin, (F) benzoic sulfimide of 600 and adds respectively the glue container, stir 30mim ~ 90min under 5 ℃～35 ℃, be uniformly dissolved fully to solid materials;

2) add (C) 0 ~ 20% Wt powder, (G) 0.01% ~ 0.1% metal ion chelation agent in the glue container, under 5 ℃～35 ℃, stir 30mim ~ 90min, even to powder lot dispersing;

3) add (H) 0.1 ~ 5% peroxide initiator, (I) 0 ~ 20% aerosil in the glue container, stir 20mim ~ 30min under 5 ℃～35 ℃, to being uniformly dispersed;

4) vacuumize except the middle bubble that removes photoresist, vacuum pressure is controlled at-0.09 ~-0.07MPa between;

5) discharging, fillingly keep in Dark Place in Low Density Polyethylene material packing, stand-by.

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