CN104610900A - Nail-free glue and preparation method thereof - Google Patents

Abstract

The invention discloses nail-free glue and a preparation method thereof, and belongs to the field of a binding agent. The nail-free glue is characterized in that the sealant consists of the following components in parts by weight: 100 parts of silane-terminated polyether, 70-140 parts of a plasticizer, 1-4 parts of a water removal agent, 0.5-4 parts of a stabilizer, 120-420 parts of filler, 3-6 parts of an adhesion accelerant and 2-5 parts of a catalyst. The product disclosed by the invention is free from volatile solvent component in a component formula, environmentally friendly and free from harm, and has performances of fast hardening, excellent mechanical property and adhesion property, heat resistance, water resistance, aging resistance and the like; and the nail-free glue can be widely applied to the binding of such base materials as stone, glass, wood, metal, plastic and the like.

Description

A kind of nail-free glue and preparation method thereof

Technical field

The invention belongs to seal gum/adhesive field, relate to a kind of nail-free glue and preparation method thereof.

Technical background

Modern architecture interior trim generally adopts the method for bond processing to replace nail or bolt, and the tackiness agent of this use is often called nail-free glue, in order to reach the object of aesthetic appeal.Timber, cement sheeting, metal, plastics, ceramic tile is comprised by sticky base material, and composite plates etc.Divide from decoration, nail-free glue is divided into aq. type, solvent-borne type and this build usually, for the ease of constructing and bondingly often using volatile solvent, comprises the organic solvent to human body and bad environmental such as aldehydes, benzene class, chlorinated organic solvent class.Divide from fluoropolymer resin and Application Areas thereof, nail-free glue can be divided into epoxy resin tackiness agent, unsaturated polyester tackiness agent, polyvinyl acetate resin adhesive stick, rubber elastomer-tackifying resin tackiness agent etc.Epoxyn has very high bonding strength, but uses curing speed comparatively slow at normal temperatures, affect constructing operation, and (lower than 10 DEG C) more should not construct at low temperatures.Unsaturated polyester-bonded dose, although have, curing speed is fast, cheap, convenient operation, but its bonding force is poor, shrinking percentage is at 10%-15%, and colloid internal stress is high, and sticking power is not strong, under wet environment, water surrounding, matrix resin can progressively be hydrolyzed, especially more obvious under the environment of acid rain, buck, and bonding strength can be caused to decline.Although polyvinyl acetate resin adhesive stick and rubber elastomer-tackifying resin tackiness agent cohesive strength high, easy construction, applied range, be exactly because containing organic solvent, after construction, smell is large, can damage HUMAN HEALTH.

Along with people's living standard constantly improves, people actively find the tackiness agent of functional, harmless, environmental protection, " green ".

Silyl-terminated polyether sealant comprehensive comparison is comprehensive, the balance of various performance is excellent, both there is good weathering resistance, weather resistance, thermotolerance, winter hardiness, cementability and covering with paint, there is again unique environment friendly, excellent low glutinous fluidity and good low temp operation.Therefore, end silane modified polyether nail-free glue, facilitate durable, cohesive force is strong, and environment-protecting asepsis, all has very strong cohesiveness to most of base material, wide application, and makes all adhesive surfaces smooth seamless, caters to environmental protection concept and the GOOD TASTE life of modern.At present, this glue obtains popularization energetically in Europe and Japan, but at home or blank out, therefore has development space and market application foreground.

Summary of the invention

Based on the pursuit that above-mentioned people are high-level to green idea, the invention provides a kind of nail-free glue that a kind of bonding strength is high, applicable base materials is wide, weather-proof, water-fast, ageing-resistant and preparation method thereof.

Object of the present invention realizes mainly through following technical proposals: a kind of nail-free glue, and the composition of raw materials of seal gum is counted by following mass parts:

Described end-silicane-group modified polyether is end group silicone-containing base polyoxytrimethylene ether, and structure is:

Wherein R and the R ' alkyl that is C1-C2, a is 3-b, b is 0 or 1, molecular weight 8000 ~ 15000.

Described softening agent is polyether glycol, and main chain contains ehter bond, and end group or side base contain the polymkeric substance being no less than 2 hydroxyls, and molecular weight, between 600 ~ 5000, comprises polyether triol, polytetrahydrofuran diol, polyether glycol or their mixture.

Described water-removal agent is vinyl-functional silicane, comprises vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methyl dimethoxysilane or their mixture.

Described stablizer is hindered amine light stabilizer or benzotriazole light stabilizer, comprises that hindered amine is oligomeric, block oligomerisation or their mixture, as two (2,2,6,6-tetramethyl--4-piperidyl) sebate etc.; Benzotriazole light stabilizer, as 2-(5-chloro (2H)-benzotriazole-2-base)-4-(methyl)-6-(tertiary butyl) phenol etc.

Described filler is the composition of the one or two or more in nano-calcium carbonate, carbon black, white carbon black, diatomite, silica powder, mica powder, titanium dioxide, kaolin.

Described adhesion promoter is organoalkoxysilane, comprises aminopropyl triethoxysilane, aminopropyl trimethoxysilane, ureidopropyltriethoxysilane, aminophenyl dimethoxysilane, glycidoxy-propyltrimethoxy silane or their mixture.

Described catalyzer is organic tin, comprises dibutyl tin laurate, stannous octoate, dibutyl two toxilic acid tin, dibutyltin diacetate, two (dodecyl sulphur) dibutyl tin or mercaptan dioctyl tins.

The preparation method of above-mentioned self cure end-silicane-group modified polyether nail-free glue, is undertaken by following processing step:

(1). by filler dry 5 ~ 20h at 120 DEG C;

(2). by end-silicane-group modified polyether 100 parts, 70 ~ 140 parts, softening agent, stablizer 0.5 ~ 4 part add in stirred autoclave

Stir, then vacuumize, continue to stir degassed 20min;

(3). stop stirring and vacuumizing;

(4). add filler 120 ~ 420 parts in batches, vacuumize in 100 ~ 110 DEG C after mixing 20min, stir degassed 1 ~ 2h;

(5). the temperature of high batch mixing step (4) obtained is down to less than 40 DEG C, is filled with nitrogen, adds water-removal agent 1 ~ 4 part, glutinous

Attached promotor 3 ~ 6 parts, mixes.

(6). under nitrogen protection condition, add catalyzer 2 ~ 5 parts, mix;

(7). vacuumize, continue to mix;

(8). inflated with nitrogen removes vacuum to normal pressure, and discharging divides and is packaged to be a kind of nail-free glue.

Step (2), (3), (4), (5), (6) and the stirred autoclave described in (7) are planetary kneader;

Step (2), (4) and the vacuum condition described in (7) are 0.090 ± 0.005MPa;

The operational condition of described planetary kneader is revolution rotating speed 25rpm;

Stirred autoclave described in step (2) is planetary kneader, and revolution rotating speed 25rpm, stirs 20min;

Stirred autoclave described in step (4) is planetary kneader, and revolution rotating speed 25rpm, stirs 1 ~ 2h;

Stirred autoclave described in step (5) is planetary kneader, and revolution rotating speed 25rpm, stirs 15 ~ 20min;

Stirred autoclave described in step (6) is planetary kneader, and revolution rotating speed 25rpm, stirs 20 ~ 30min.

End-silicane-group modified polyether nail-free glue non-volatility solvent prepared by the present invention, environmental protection is without harm, and bonding strength is high, applicable base materials is wide, weather-proof, water-fast, ageing-resistant, has extraordinary application prospect.

Embodiment

For understanding the present invention further, be described a kind of nail-free glue provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.

Embodiment 1

Nano-calcium carbonate is placed in constant temperature oven dry 20h at 120 DEG C; By end-silicane-group modified polyether 100 parts, Polyoxypropylene diol 80 parts, two (2,2,6,6-tetramethyl--4-piperidyl) sebate 2 parts add in planetary kneader, then vacuumize, and continue to stir degassed 20min; Stop stirring and vacuumizing, add nano-calcium carbonate filler 60 and 70 parts in batches, after mixing, be evacuated to 0.090 ± 0.005MPa in 100 ~ 110 DEG C, stir degassed 1 ~ 2h; The temperature of the high batch mixing obtained is down to less than 50 DEG C, is filled with nitrogen, add vinyltrimethoxy silane 1.5 parts, adhesion promoter aminopropyl triethoxysilane 3 parts, mix.Under nitrogen protection condition, add catalyst dibutyltin dilaurylate 2 parts, mix; Vacuumize, continue to mix; Inflated with nitrogen removes vacuum to normal pressure, and discharging divides and is packaged to be nail-free glue.

Table 1 embodiment 1 Raw composition and mass parts

Embodiment 2

The preparation method of this seal gum is as embodiment 1.

Table 2 embodiment 2 Raw composition and mass parts

Embodiment 3

The preparation method of this seal gum is as embodiment 1.

Table 3 embodiment 3 Raw composition and mass parts

Embodiment 4

The preparation method of this seal gum is as embodiment 1.

Table 4 embodiment 4 Raw composition and mass parts

Embodiment 5

The preparation method of this seal gum is as embodiment 1.

Table 5 embodiment 5 Raw composition and mass parts

Detected by the nail-free glue that embodiment 1 ~ embodiment 5 prepares, table 6 lists the test result of sealing glue.

The test result of table 6 nail-free glue compares

Performance	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
						Denseness	340	300	270	220	250
100% modulus (MPa)	1.12	1.26	1.15	0.93	0.73
						Tensile strength (MPa)	1.75	1.84	1.50	1.31	1.05
Elongation at break (%)	320	350	290	230	190

Claims (10)

1. a nail-free glue, is characterized in that: the composition of raw materials of described seal gum is according to the mass fraction:

2., by a kind of nail-free glue according to claim 1, it is characterized in that: described end-silicane-group modified polyether is end group silicone-containing base polyoxytrimethylene ether, and structure is:

Wherein R and the R ' alkyl that is C1-C2, a is 3-b, b is 0 or 1, molecular weight 8000 ~ 15000.

3., by a kind of nail-free glue according to claim 1, it is characterized in that: described softening agent is polyether glycol, and main chain contains ehter bond, end group or side base contain the polymkeric substance being no less than 2 hydroxyls, and molecular weight is between 600 ~ 5000.

4., by a kind of nail-free glue described in claim 1 or 3, it is characterized in that: described polyether glycol comprises polyether triol, polytetrahydrofuran diol, polyether glycol or their mixture.

5., by a kind of nail-free glue according to claim 1, it is characterized in that: described water-removal agent is vinyl-functional silicane, comprise vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methyl dimethoxysilane or their mixture.

6., by a kind of nail-free glue according to claim 1, it is characterized in that: described stablizer is hindered amine light stabilizer or benzotriazole light stabilizer.

7. by hindered amine light stabilizer described in claim 1 or 6, it is characterized in that: described hindered amine light stabilizer comprises low-molecular-weight hindered amine light stabilizer, the hindered amine as light stabilizer of block oligomerisation or poly-hindered amine composite synergistic stablizer etc.

8., by a kind of nail-free glue according to claim 1, it is characterized in that: described filler is the composition of the one or two or more in nano-calcium carbonate, carbon black, white carbon black, diatomite, silica powder, mica powder, titanium dioxide, kaolin.

9. by a kind of nail-free glue according to claim 1, it is characterized in that: described adhesion promoter is organoalkoxysilane, comprise aminopropyl triethoxysilane, aminopropyl trimethoxysilane, ureidopropyltriethoxysilane, aminophenyl dimethoxysilane, glycidoxy-propyltrimethoxy silane or their mixture, described catalyzer is organic tin, comprises dibutyl tin laurate, stannous octoate, dibutyl two toxilic acid tin, dibutyltin diacetate, two (dodecyl sulphur) dibutyl tin or mercaptan dioctyl tins.

10. a preparation method for nail-free glue, is characterized in that: undertaken by following processing step:

(1). by filler dry 5 ~ 20h at 120 DEG C;

(2). by end-silicane-group modified polyether 100 parts, 70 ~ 140 parts, softening agent, stablizer 0.5 ~ 4 part add in stirred autoclave and stir, and then vacuumize, and continue to stir degassed 20min;

(3). stop stirring and vacuumizing;

(4). add filler 120 ~ 420 parts in batches, vacuumize in 100 ~ 110 DEG C after mixing 20min, stir degassed 1 ~ 2h;

(5). the temperature of high batch mixing step (4) obtained is down to less than 40 DEG C, is filled with nitrogen, adds water-removal agent 1 ~ 4 part, and adhesion promoter 3 ~ 6 parts, mixes.

(6). under nitrogen protection condition, add catalyzer 2 ~ 5 parts, mix;

(7). vacuumize, continue to mix;

(8). inflated with nitrogen removes vacuum to normal pressure, and discharging divides and is packaged to be a kind of nail-free glue.