CN105400237A - Surface treatment method for nanometer calcium carbonate applied to fill silicone sealant - Google Patents
Surface treatment method for nanometer calcium carbonate applied to fill silicone sealant Download PDFInfo
- Publication number
- CN105400237A CN105400237A CN201510945104.4A CN201510945104A CN105400237A CN 105400237 A CN105400237 A CN 105400237A CN 201510945104 A CN201510945104 A CN 201510945104A CN 105400237 A CN105400237 A CN 105400237A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- nano
- surface treatment
- silicone sealant
- nanometer calcium
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A disclosed surface treatment method for nanometer calcium carbonate applied to fill a silicone sealant comprises the following steps: adding a nanometer calcium carbonate slurry into a reaction kettle, stirring and heating to 60-80 DEG C, so as to obtain a nanometer calcium carbonate suspending slurry; slowly adding a compound surfactant composed of saturated aliphatic acid and coconut oil into the nanometer calcium carbonate suspending slurry for first surface treatment; then slowly adding an alkylphenol polyoxyethylene ether dimeric surfactant for secondary surface treatment, so as to obtain a nanometer calcium carbonate modification solution; and performing dewatering, drying, crushing and sieving on the nanometer calcium carbonate modification solution, so as to obtain the nanometer calcium carbonate for filling the silicone sealant. The nanometer calcium carbonate obtained according to the surface treatment method possesses good dispersibility, hydrophobicity and relatively low oil absorption value, and is capable of improving the storage stability, mechanical properties, ageing resistance, photothermy resistance, oxidation resistance and other performances of the silicone sealant when being applied to fill the silicone sealant.
Description
Technical field
The present invention relates to field of inorganic material preparing technology, specifically a kind of surface treatment method being applied to the nano-calcium carbonate of filling silicone sealant.
Background technology
Nano-calcium carbonate is as a kind of new type functional inorganic materials, its ultra-fine particle diameter and high-specific surface area area make it have the unexistent quantum size effect of general mineral filler, small-size effect, surface effects and macroscopic quantum effect, stable performance in addition, easily processing and cheap and be used for the industries such as rubber plastic, coating and printing ink, papermaking and silicone sealant by wide shipping.But the nano-calcium carbonate of long time without surface modification surface oleophilic drainage, is difficult to be scattered among matrix material uniformly; And specific surface area is large, surface energy is high, and easily interparticle reunion occurs, such defect constrains nano-calcium carbonate use in the industry, therefore carries out surface modification to nano-calcium carbonate imperative.
Single-component silicone sealant is mainly base-material with polysiloxane base polymer, be aided with that linking agent, coupling agent, catalyzer and filler etc. mix, and can with reaction of moisture in air become elastomeric a kind of sealing material after contacting with air.As sealing material, silicone sealant have can self cure, wet-heat resisting, anti-extrusion, smell little pollution-free and all can the feature of bonds well with multiple base material, be used widely in industries such as building, automobile, solar components and medical treatment; But its also exist the shelf lives short, there is the defects such as Hardening crack at outdoor environment by oxidizable degraded after photo-thermal, higher service requirements can not be met.The filler that nano-calcium carbonate is commonly used the most as single-component silicone sealant, the quality of its performance will affect the quality of silicone sealant, therefore, provides a kind of nano-calcium carbonate possessing excellent properties to can be high performance silicon ketone seal gum and lays a good foundation.
Chinese patent CN101863503A discloses a kind of preparation method of nanometer calcium carbonate for the application of high-grade silicone adhesive, and the method comprises calcining and digestion reaction, carburizing reagent, one-time surface process, secondary surface preparation, dehydrate and the step such as crushing and classification, three subsurface process, separating twice process.The method by controlling the initial of carburizing reagent and end reaction temperature, thus ensure that the dispersiveness of nano-calcium carbonate; Use grease, saturated fatty acid and salt thereof and unsaturated fatty acids and salt thereof to carry out three subsurface modifications simultaneously, ensure its coated homogeneity.Use the silicone sealant after modification gained nanon calcium carbonatefilled to have good dispersiveness, thixotropy and cohesiveness, but its depot and anti-light thermal oxidation still can not get improving, when outdoor application, product performance are undesirable.
Chinese invention patent CN104893361A discloses the Nano calcium carbonate dedicated preparation method of a kind of sealing neutral silicone resin, this invention with Sorbitol Powder and polycarboxylate sodium for dispersion agent, secondary carbonization and emulsion dispersion are carried out to calcium hydroxide slurry, re-use dimeracid and stearic acid and the saponified of NaOH saponification gained and surface treatment is carried out to the ripe slurry of calcium carbonate, thus obtain active nano-calcium carbonate.The silicone sealant that the method obtains has good resistance to light thermal property, water resistance and cohesive strength, but its storage period is short, and end properties is unstable.
Therefore, study a kind ofly can give that single-component dealcoholization-type silicone sealant is well fast light, the nano-calcium carbonate surface treatment method of thermal oxidation and package stability is very important.
Summary of the invention
The object of the invention is to the nano-calcium carbonate Problems existing for existing filling silicone sealant, a kind of surface treatment method being applied to the nano-calcium carbonate of filling silicone sealant is provided, nano-calcium carbonate activity after use the method surface modification is high, stable performance, after filling as filler, while ensureing that silicone sealant has good processing characteristics and mechanical property, also give silicone sealant good storage stability and ageing-resistant performance.
The present invention mainly realizes based on following principle:
Be 23.0 ~ 38.0m by specific surface area
2/ g nano-calcium carbonate filler saturated fatty acid and Oleum Cocois built agent carry out one-time surface process, then carry out secondary surface preparation with alkylphenol polyoxyethylene ether Gemini surface active agent.Alkylphenol polyoxyethylene ether used in the present invention can be used as reductive agent, suppresses the oxidation of seal gum.After using alkylphenol polyoxyethylene ether to carry out surface treatment; filling surface is evenly coated with carbon-oxygen bond; and siloxane bond is more stable than carbon-oxygen bond; silica chain is protected by the carbon oxygen chain of sacrificing in alkylphenol polyoxyethylene ether molecule in seal gum weathering process; thus raising shelf characteric, slow down aging speed.Secondly the aliphatic chain oleophylic in alkylphenol polyoxyethylene ether molecule, can connect with polysiloxane chain and form physics cross-linking set, and carbon oxygen chain in alkylphenol polyoxyethylene ether molecule is hydrophilic, easily be adsorbed in calcium carbonate surface, also the cohesiveness improving seal gum and bonding base material is contributed to, be coated between the ehter bond of calcium carbonate surface and siloxanes simultaneously and can form hydrogen bond, be conducive to improving seal gum thixotropy.
In order to realize above object, the technical solution used in the present invention is as follows:
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) nano-calcium carbonate slurries are added reactor, stir, and be heated to 60 ~ 80 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation slowly add to nano-calcium carbonate suspension slurry and carry out one-time surface process with the composite surface treatment agent of saturated fatty acid and Oleum Cocois composition, continue stirring 15 ~ 30min, obtain the preliminary modification liquid of nano-calcium carbonate; The consumption of described composite surface treatment agent is 2.0 ~ 3.5% of calcium carbonate dry matrix amount;
(3) slowly add alkylphenol polyoxyethylene ether Gemini surface active agent in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) and carry out secondary surface preparation, its add-on is 0.5 ~ 2.0% of nano-calcium carbonate butt quality, stir 25 ~ 60min, obtain nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 100 ~ 130 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, sieve, namely obtain the nano-calcium carbonate of filling silicone sealant
Further, above-described nano-calcium carbonate specific surface area is 23.0 ~ 38.0m
2/ g.
Further, above-described alkylphenol polyoxyethylene ether Gemini surface active agent is that alkylphenol and oxyethane carry out ethoxylation and is polymerized, comprising the polymkeric substance of a kind of and oxyethane in butane group phenol, sim alkylphenol, nonyl phenol, 4-dodecylphenol, its molecular structural formula is:
Wherein: n is greater than 0 and is less than or equal to 12, m and is greater than 0 and is less than or equal to 16.
Further, the composite surface treatment agent described in above step (2) is that the saturated fatty acid of 2 ~ 4:1 and Oleum Cocois form by mass ratio; The C atom number of described saturated fatty acid is 16 ~ 20, comprising one or more in palmitinic acid, stearic acid and eicosanoic acid.
Further, the preparation method of above-described composite surface treatment agent: saturated fatty acid and Oleum Cocois are added reactor with the mass ratio of 2 ~ 4:1, be incorporated as the sodium hydroxide of saturated fatty acid quality 12 ~ 15% again, control to carry out saponification reaction at 75 ~ 95 DEG C, obtain composite surface treatment agent.
The nano-calcium carbonate calcium product dispersiveness obtained through surface treatment of the present invention is fabulous, is applied to when filling silicone sealant, can improves the package stability of silicone sealant, mechanics, ageing-resistant, anti-light heat, the performance such as anti-oxidant.
Compared with prior art, beneficial effect of the present invention:
1, the inventive method first carries out one-time surface process with saturated fatty acid and Oleum Cocois built agent, recycling alkylphenol polyoxyethylene ether Gemini surface active agent carries out secondary surface preparation, the nano-calcium carbonate calcium product obtained has good dispersiveness, hydrophobicity and lower oil-absorption(number), be applied to filling silicone sealant, the package stability of silicone sealant, mechanics, ageing-resistant, anti-light heat, the performance such as anti-oxidant can be improved.
2, alkylphenol polyoxyethylene ether used in the present invention can be used as reductive agent, can suppress the oxidation of seal gum; After using alkylphenol polyoxyethylene ether to carry out secondary surface preparation, filling surface is evenly coated with carbon-oxygen bond, and siloxane bond is more stable than carbon-oxygen bond, silica chain is protected by the carbon oxygen chain of sacrificing in alkylphenol polyoxyethylene ether molecule in seal gum weathering process, thus raising shelf characteric, slow down aging speed; Secondly the aliphatic chain oleophylic in alkylphenol polyoxyethylene ether molecule, can connect with polysiloxane chain and form physics cross-linking set, and carbon oxygen chain in alkylphenol polyoxyethylene ether molecule is hydrophilic, easily be adsorbed in calcium carbonate surface, also the cohesiveness improving seal gum and bonding base material is contributed to, be coated between the ehter bond of calcium carbonate surface and siloxanes simultaneously and can form hydrogen bond, be conducive to improving seal gum thixotropy.
3, simple, the easily operation of the inventive method technique, production cost are low, have good economic benefit and social benefit, easily realize suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is further described, but be not limited to protection scope of the present invention.
The preparation of the nano-calcium carbonate slurries described in following examples:
(1) diluted by the milk of lime after refining, ageing 36-72h, proportion is adjusted to 1.055-1.070, and control temperature is 20-26 DEG C, is then transported to the bubbling carbonizing tower with stirring;
(2) pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 6-10m3/h, and carbonic acid gas volume content is 25-35%, when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area controls as 20-40m
2/ g.
embodiment 1
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) be 30m by specific surface
2the nano-calcium carbonate slurries of/g add reactor, stir, and are heated to 75 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation to nano-calcium carbonate suspension slurry slowly add with stearic acid and Oleum Cocois composition composite surface treatment agent carry out one-time surface process, its add-on is 3.0% of calcium carbonate dry matrix amount, continue to stir 15min, obtain the preliminary modification liquid of nano-calcium carbonate;
The preparation method of the above composite surface treatment agent: stearic acid and Oleum Cocois are added reactor with the mass ratio of 3:1, then is incorporated as the sodium hydroxide of stearic acid quality 15%, controls to carry out saponification reaction at 80 DEG C, obtains composite surface treatment agent.
(3) the octyl phenol polyoxyethylene ether Gemini surface active agent being slowly incorporated as 1.5% of nano-calcium carbonate butt quality in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) carries out secondary surface preparation, stir 45min, obtain nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 120 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, cross 100 mesh sieves, namely obtain the nano-calcium carbonate of filling silicone sealant.
embodiment 2
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) be 23m by specific surface
2the nano-calcium carbonate slurries of/g add reactor, stir, and are heated to 60 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation to nano-calcium carbonate suspension slurry slowly add with palmitinic acid and Oleum Cocois composition composite surface treatment agent carry out one-time surface process, its add-on is 2.5% of calcium carbonate dry matrix amount, continue to stir 20min, obtain the preliminary modification liquid of nano-calcium carbonate;
The preparation method of the above composite surface treatment agent: palmitinic acid and Oleum Cocois are added reactor with the mass ratio of 2:1, then is incorporated as the sodium hydroxide of palmitinic acid quality 12%, controls to carry out saponification reaction at 90 DEG C, obtains composite surface treatment agent.
(3) the octyl phenol polyoxyethylene ether Gemini surface active agent being slowly incorporated as nano-calcium carbonate butt quality 2.0% in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) carries out secondary surface preparation, stir 30min, obtain nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 110 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, cross 100 mesh sieves, namely obtain the nano-calcium carbonate of filling silicone sealant.
embodiment 3
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) be 30m by specific surface
2the nano-calcium carbonate slurries of/g add reactor, stir, and are heated to 70 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation to nano-calcium carbonate suspension slurry slowly add with eicosanoic acid and Oleum Cocois composition composite surface treatment agent carry out one-time surface process, its add-on is 3.0% of calcium carbonate dry matrix amount, continue to stir 20min, obtain the preliminary modification liquid of nano-calcium carbonate;
The preparation method of the above composite surface treatment agent: eicosanoic acid and Oleum Cocois are added reactor with the mass ratio of 4:1, then is incorporated as the sodium hydroxide of eicosanoic acid quality 13%, controls to carry out saponification reaction at 95 DEG C, obtains composite surface treatment agent.
(3) the butylphenol polyoxyethylene ether Gemini surface active agent being slowly incorporated as nano-calcium carbonate butt quality 1.5% in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) carries out secondary surface preparation, stir 25min, obtain nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 130 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, cross 100 mesh sieves, namely obtain the nano-calcium carbonate of filling silicone sealant.
embodiment 4
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) be 35m by specific surface
2the nano-calcium carbonate slurries of/g add reactor, stir, and are heated to 80 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation to nano-calcium carbonate suspension slurry slowly add with eicosanoic acid, stearic acid and Oleum Cocois composition composite surface treatment agent carry out one-time surface process, its add-on is 3.5% of calcium carbonate dry matrix amount, continue to stir 25min, obtain the preliminary modification liquid of nano-calcium carbonate;
The preparation method of the above composite surface treatment agent: eicosanoic acid, stearic acid and Oleum Cocois are added reactor with the mass ratio of 2:1:1, be incorporated as the sodium hydroxide of saturated fatty acid quality 15% again, control to carry out saponification reaction at 85 DEG C, obtain composite surface treatment agent.
(3) the nonylphenol polyoxyethylene ether Gemini surface active agent being slowly incorporated as nano-calcium carbonate butt quality 0.5% in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) carries out secondary surface preparation, stir 60min, obtain nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 120 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, cross 100 mesh sieves, namely obtain the nano-calcium carbonate of filling silicone sealant.
embodiment 5
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) be 38m by specific surface
2the nano-calcium carbonate slurries of/g add reactor, stir, and are heated to 70 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation to nano-calcium carbonate suspension slurry slowly add with stearic acid and Oleum Cocois composition composite surface treatment agent carry out one-time surface process, its add-on is 2.0% of calcium carbonate dry matrix amount, continue to stir 20min, obtain the preliminary modification liquid of nano-calcium carbonate;
The preparation method of the above composite surface treatment agent: stearic acid and Oleum Cocois are added reactor with the mass ratio of 4:1, then is incorporated as the sodium hydroxide of stearic acid quality 12%, controls to carry out saponification reaction at 80 DEG C, obtains composite surface treatment agent.
(3) the dodecyl phenol polyoxyethylene ether Gemini surface active agent being slowly incorporated as nano-calcium carbonate butt quality 1.0% in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) carries out secondary surface preparation, stir 40min, obtain nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 110 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, cross 100 mesh sieves, namely obtain the nano-calcium carbonate of filling silicone sealant.
comparative example 1
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) be 30m by specific surface
2the nano-calcium carbonate slurries of/g add reactor, stir, and are heated to 75 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation to nano-calcium carbonate suspension slurry slowly add with stearic acid and Oleum Cocois composition composite surface treatment agent carry out one-time surface process, its add-on is 3% of nano-calcium carbonate butt weight, continue to stir 15min, obtain the preliminary modification liquid of nano-calcium carbonate;
The preparation method of the above composite surface treatment agent: stearic acid and Oleum Cocois are added reactor with the mass ratio of 3:1, then is incorporated as the sodium hydroxide of stearic acid quality 15%, controls to carry out saponification reaction at 80 DEG C, obtains composite surface treatment agent.
(3) the behenic acid tensio-active agent being slowly incorporated as nano-calcium carbonate butt quality 1.5% in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) carries out secondary surface preparation, stirs 45min, obtains nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 120 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, cross 100 mesh sieves, namely obtain the nano-calcium carbonate of filling silicone sealant.
comparative example 2
Be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, comprise the following steps:
(1) be 30m by specific surface
2the nano-calcium carbonate slurries of/g add reactor, stir, and are heated to 75 DEG C, obtain nano-calcium carbonate suspension slurry;
(2) under agitation to nano-calcium carbonate suspension slurry slowly add with stearic acid and Oleum Cocois composition composite surface treatment agent carry out one-time surface process, its add-on is 3% of nano-calcium carbonate butt weight, continue to stir 15min, obtain the preliminary modification liquid of nano-calcium carbonate;
The preparation method of the above composite surface treatment agent: stearic acid and Oleum Cocois are added reactor with the mass ratio of 3:1, then is incorporated as the sodium hydroxide of stearic acid quality 15%, controls to carry out saponification reaction at 80 DEG C, obtains composite surface treatment agent.
(3) the lauric acid tensio-active agent being slowly incorporated as nano-calcium carbonate butt quality 1.5% in the preliminary modification liquid of nano-calcium carbonate obtained to step (2) carries out secondary surface preparation, stirs 45min, obtains nono calcium carbonate modified liquid;
(4) by nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 120 DEG C, obtains dried material;
(5) dried material is passed through pulverizing again, cross 100 mesh sieves, namely obtain the nano-calcium carbonate of filling silicone sealant.
the application test of embodiment and comparative example product
The nano-calcium carbonate product application each embodiment and comparative example surface treatment obtained is in the filling of silicone sealant, and the concrete formula preparing silicone sealant is as shown in table 1.
table 1: nano-calcium carbonate is applied to prepares silicone sealant formula
| Component | Mass parts |
| Hydroxyl-terminated injecting two methyl siloxane | 100 |
| Nano-calcium carbonate | 120 |
| Softening agent | 12 |
| Linking agent | 5 |
| Coupling agent | 0.8 |
| Catalyzer | 2.5 |
| Stablizer | 1 |
Softening agent in above-mentioned formula is dimethyl silicone oil, linking agent is methyltrimethoxy silane (D-20), coupling agent is γ-aminopropyltrimethoxysilane (KH-550), catalyzer is 2.0 part two (methyl aceto acetate) two (isopropoxy) titanic acid ester complex compound and 0.5 part of dibutyl tin laurate, and stablizer is the mixture of 0.5 part of trimethyl silicane ethyl propionate and 0.5 part of carbimide propyl-triethoxysilicane.
The preparation method of silicone silicone sealant of the present invention is as follows:
Take each raw material by mass fraction, load weighted hydroxyl-terminated injecting two methyl siloxane, active nano-calcium carbonate and softening agent put into planetary stirrer, vacuum tightness be-0.085MPa, temperature dewaters under being the condition of 130 DEG C 2h, and base-material is mixed; Make base-material be cooled to 30 ~ 40 DEG C under vacuum conditions, in system, add linking agent, coupling agent, catalyzer and stablizer successively, discharging tinning after Homogeneous phase mixing 30min, can obtain silicone sealant product under vacuum conditions.Through detecting the product performance of silicone sealant, detected result is as shown in table 2.
table 2: nano-calcium carbonate is applied to the product performance of filling silicone sealant
Be applied to silicone sealant through the inventive method surface-treated nano-calcium carbonate as can be seen from the table to fill, the package stability of the silicone sealant of preparation, mechanics, ageing-resistant, anti-light heat and antioxidant property are all very excellent.
Claims (4)
1. be applied to a surface treatment method for the nano-calcium carbonate of filling silicone sealant, it is characterized in that: comprise the following steps:
Nano-calcium carbonate slurries are added reactor, stirs, and be heated to 60 ~ 80 DEG C, obtain nano-calcium carbonate suspension slurry;
Under agitation slowly add to nano-calcium carbonate suspension slurry and carry out one-time surface process with the composite surface treatment agent of saturated fatty acid and Oleum Cocois composition, continue stirring 15 ~ 30min, obtain the preliminary modification liquid of nano-calcium carbonate; The consumption of described composite surface treatment agent is 2.0 ~ 3.5% of calcium carbonate dry matrix amount;
In the preliminary modification liquid of nano-calcium carbonate that step (2) obtains, slowly add alkylphenol polyoxyethylene ether Gemini surface active agent carry out secondary surface preparation, its add-on is 0.5 ~ 2.0% of nano-calcium carbonate butt quality, stir 25 ~ 60min, obtain nono calcium carbonate modified liquid;
By nono calcium carbonate modified liquid filter-press dehydration, dry through chain band drying machine, drying temperature is 100 ~ 130 DEG C, obtains dried material;
By dried material again through pulverizing, sieving, namely obtaining the nano-calcium carbonate of filling silicone sealant.
2. a kind of surface treatment method being applied to the nano-calcium carbonate of filling silicone sealant according to claim 1, it is characterized in that: described alkylphenol polyoxyethylene ether Gemini surface active agent is that alkylphenol and oxyethane carry out ethoxylation and is polymerized, comprising the polymkeric substance of a kind of and oxyethane in butane group phenol, sim alkylphenol, nonyl phenol, 4-dodecylphenol, its molecular structural formula is:
Wherein: n is greater than 0 and is less than or equal to 12, m and is greater than 0 and is less than or equal to 16.
3. be according to claim 1ly a kind ofly applied to the surface treatment method of nano-calcium carbonate of filling silicone sealant, it is characterized in that: the composite surface treatment agent described in step (2) is that the saturated fatty acid of 2 ~ 4:1 and Oleum Cocois form by mass ratio; The C atom number of described saturated fatty acid is 16 ~ 20, comprising one or more in palmitinic acid, stearic acid and eicosanoic acid.
4. a kind of surface treatment method being applied to the nano-calcium carbonate of filling silicone sealant according to claim 3, it is characterized in that: the preparation method of described composite surface treatment agent: saturated fatty acid and Oleum Cocois are added reactor with the mass ratio of 2 ~ 4:1, be incorporated as the sodium hydroxide of saturated fatty acid quality 12 ~ 15% again, control temperature carries out saponification reaction at 75 ~ 95 DEG C, obtains composite surface treatment agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510945104.4A CN105400237B (en) | 2015-12-17 | 2015-12-17 | A kind of surface treatment method for the nano-calcium carbonate for being applied to filling silicone sealant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510945104.4A CN105400237B (en) | 2015-12-17 | 2015-12-17 | A kind of surface treatment method for the nano-calcium carbonate for being applied to filling silicone sealant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105400237A true CN105400237A (en) | 2016-03-16 |
| CN105400237B CN105400237B (en) | 2018-02-16 |
Family
ID=55466014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510945104.4A Active CN105400237B (en) | 2015-12-17 | 2015-12-17 | A kind of surface treatment method for the nano-calcium carbonate for being applied to filling silicone sealant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105400237B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778568A (en) * | 2016-04-18 | 2016-07-20 | 安徽省宣城市华纳新材料科技有限公司 | Surface treatment method for nano calcium carbonate special for photovoltaic adhesive |
| CN106675110A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | High-activity nano-calcium carbonate |
| CN108017937A (en) * | 2017-12-15 | 2018-05-11 | 广西华纳新材料科技有限公司 | Preparation method for silane modified polyether seal glue calcium carbonate |
| CN106700657B (en) * | 2016-11-21 | 2018-10-23 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of thermostable silicone glue nano-calcium carbonate |
| CN109628045A (en) * | 2018-12-19 | 2019-04-16 | 安徽省宣城市华纳新材料科技有限公司 | A kind of nanometer calcium carbonate for silane modified polyether seal glue |
| CN110229542A (en) * | 2019-07-22 | 2019-09-13 | 恩平燕怡新材料有限公司 | A kind of PVC pipe nm-class active calcium carbonate and preparation method thereof, PVC pipe |
| CN110423341A (en) * | 2019-08-09 | 2019-11-08 | 山东益丰生化环保股份有限公司 | A kind of polyether amine compound and preparation method thereof, gasoline cleaning agent |
| CN111253884A (en) * | 2020-03-16 | 2020-06-09 | 广东翔龙科技股份有限公司 | Application of micron calcium carbonate in sealant |
| CN112374520A (en) * | 2020-11-27 | 2021-02-19 | 广西华纳新材料科技有限公司 | Preparation method of active calcium carbonate for moisture-curing polyurethane sealant |
| CN112724709A (en) * | 2021-01-23 | 2021-04-30 | 广西碳酸钙产业化工程院有限公司 | Special heavy calcium carbonate for silicone sealant and preparation method thereof |
| CN112898942A (en) * | 2021-01-23 | 2021-06-04 | 广西碳酸钙产业化工程院有限公司 | Special heavy calcium carbonate for endowing single-component dealcoholized silicone sealant with good flame retardant property and preparation method thereof |
| CN115849425A (en) * | 2022-12-09 | 2023-03-28 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174275A (en) * | 2011-03-15 | 2011-09-07 | 广西华纳新材料科技有限公司 | Surface modification method for nano calcium carbonate |
| CN102491397A (en) * | 2011-12-09 | 2012-06-13 | 广东嘉维化工实业有限公司 | Preparation method of nano-calcium carbonate SCC-2 special for silicone sealant |
| CN103432958A (en) * | 2013-08-22 | 2013-12-11 | 郑四荣 | Calcium carbonate surface-active agent |
| CN103693669A (en) * | 2013-12-03 | 2014-04-02 | 恩平市嘉维化工实业有限公司 | Method for preparing nano calcium carbonate special for rolling film |
| CN104893361A (en) * | 2015-05-25 | 2015-09-09 | 福建鸿丰纳米科技有限公司 | Preparation method of nano calcium carbonate special for neutral silicone sealant |
-
2015
- 2015-12-17 CN CN201510945104.4A patent/CN105400237B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174275A (en) * | 2011-03-15 | 2011-09-07 | 广西华纳新材料科技有限公司 | Surface modification method for nano calcium carbonate |
| CN102491397A (en) * | 2011-12-09 | 2012-06-13 | 广东嘉维化工实业有限公司 | Preparation method of nano-calcium carbonate SCC-2 special for silicone sealant |
| CN103432958A (en) * | 2013-08-22 | 2013-12-11 | 郑四荣 | Calcium carbonate surface-active agent |
| CN103693669A (en) * | 2013-12-03 | 2014-04-02 | 恩平市嘉维化工实业有限公司 | Method for preparing nano calcium carbonate special for rolling film |
| CN104893361A (en) * | 2015-05-25 | 2015-09-09 | 福建鸿丰纳米科技有限公司 | Preparation method of nano calcium carbonate special for neutral silicone sealant |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778568B (en) * | 2016-04-18 | 2018-05-01 | 安徽省宣城市华纳新材料科技有限公司 | A kind of Nano calcium carbonate dedicated surface treatment method of photovoltaic glue |
| CN105778568A (en) * | 2016-04-18 | 2016-07-20 | 安徽省宣城市华纳新材料科技有限公司 | Surface treatment method for nano calcium carbonate special for photovoltaic adhesive |
| CN106675110A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | High-activity nano-calcium carbonate |
| CN106700657B (en) * | 2016-11-21 | 2018-10-23 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of thermostable silicone glue nano-calcium carbonate |
| CN108017937A (en) * | 2017-12-15 | 2018-05-11 | 广西华纳新材料科技有限公司 | Preparation method for silane modified polyether seal glue calcium carbonate |
| CN108017937B (en) * | 2017-12-15 | 2020-06-23 | 广西华纳新材料科技有限公司 | Preparation method of silane modified polyether sealant calcium carbonate |
| CN109628045B (en) * | 2018-12-19 | 2020-12-04 | 安徽省宣城市华纳新材料科技有限公司 | Nano calcium carbonate for silane modified polyether sealant |
| CN109628045A (en) * | 2018-12-19 | 2019-04-16 | 安徽省宣城市华纳新材料科技有限公司 | A kind of nanometer calcium carbonate for silane modified polyether seal glue |
| CN110229542A (en) * | 2019-07-22 | 2019-09-13 | 恩平燕怡新材料有限公司 | A kind of PVC pipe nm-class active calcium carbonate and preparation method thereof, PVC pipe |
| CN110423341A (en) * | 2019-08-09 | 2019-11-08 | 山东益丰生化环保股份有限公司 | A kind of polyether amine compound and preparation method thereof, gasoline cleaning agent |
| CN111253884A (en) * | 2020-03-16 | 2020-06-09 | 广东翔龙科技股份有限公司 | Application of micron calcium carbonate in sealant |
| CN111253884B (en) * | 2020-03-16 | 2021-10-15 | 广东翔龙科技股份有限公司 | Application of micron calcium carbonate in sealant |
| CN112374520A (en) * | 2020-11-27 | 2021-02-19 | 广西华纳新材料科技有限公司 | Preparation method of active calcium carbonate for moisture-curing polyurethane sealant |
| CN112724709A (en) * | 2021-01-23 | 2021-04-30 | 广西碳酸钙产业化工程院有限公司 | Special heavy calcium carbonate for silicone sealant and preparation method thereof |
| CN112898942A (en) * | 2021-01-23 | 2021-06-04 | 广西碳酸钙产业化工程院有限公司 | Special heavy calcium carbonate for endowing single-component dealcoholized silicone sealant with good flame retardant property and preparation method thereof |
| CN115849425A (en) * | 2022-12-09 | 2023-03-28 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105400237B (en) | 2018-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105400237A (en) | Surface treatment method for nanometer calcium carbonate applied to fill silicone sealant | |
| CN106700657B (en) | A kind of surface treatment method of thermostable silicone glue nano-calcium carbonate | |
| CN104087029B (en) | A kind of preparation method of silicone sealant special active calcium carbonate | |
| CN102516821B (en) | Surface modification method of nano-grade calcium carbonate used in room-temperature vulcanized silicone adhesive | |
| CN104479411A (en) | Surface modification method of special nano calcium carbonate for silicone sealants | |
| CN103613955B (en) | Method for preparing special nano calcium carbonate (nano-CaCO3) for vehicle adhesive | |
| CN108529923B (en) | Modified cement grinding aid and preparation method thereof | |
| CN109776022B (en) | Composite controllable hydration cement-based material and application thereof | |
| CN104497634A (en) | Preparation method of nano calcium carbonate used for weather proofing silicone sealant | |
| CN104497633A (en) | Nano calcium carbonate surface treatment method | |
| CN108165230B (en) | Single-component silane modified sealant for industrialized building | |
| CN111154453A (en) | Heat-resistant single-component addition type organic silicon adhesive and preparation method thereof | |
| CN103665937A (en) | Method for preparing nano calcium carbonate specially used for middle and top grade silicone sealants | |
| CN106634049A (en) | Method for preparing nano calcium carbonate for weather-resistant ink | |
| CN107641494A (en) | A kind of coupling agent modified fluid sealant of α isocyanato silanes | |
| CN109651975A (en) | A kind of preparation method of two-component silane modified polyether seal glue nanometer calcium carbonate | |
| CN105060306B (en) | Preparation method of silica nanotube | |
| CN109082245B (en) | Preparation method of nano calcium carbonate for single-component MS glue | |
| CN113388245B (en) | Waterproof leaking stoppage grouting material and preparation method and application thereof | |
| CN105400238B (en) | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste | |
| CN112724924B (en) | Silicone structural adhesive for hollow glass and preparation method thereof | |
| CN108795317A (en) | The method of modifying of silicone sealant nano-calcium carbonate | |
| CN105524489A (en) | In-situ emulsification modification method for nano calcium carbonate for polyurethane sealant | |
| CN104371638A (en) | One-component ketoxime removal type sealant and preparation method thereof | |
| CN108977166A (en) | A kind of silicone sealant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 530103 No.29, Ganwei street, Ganwei Town, Wuming District, Nanning City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Warner New Material Co.,Ltd. Address before: 530103 No.29, Ganwei street, Ganwei Town, Wuming County, Nanning City, Guangxi Zhuang Autonomous Region Patentee before: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. |
|
| CP03 | Change of name, title or address |