CN109777281A - A kind of stone protectant and preparation method thereof - Google Patents
A kind of stone protectant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of stone protectants and preparation method thereof, belong to stone protector field.Reinforcement protection agent and former stone material, which is added, in the present invention good compatibility and binding force, carries out hardening reinforcement protection to stone material surface layer；Additive of self-rehabilitation is added when being led to glue film breakage by external force, the macromolecular chain in the reversibility and protection film forming layer of oxime key forms crosslinking again and heals, and re-forms restoration and protection layer, carries out the selfreparing of stone surface；Osmotically active agent is added, so that protective agent, which can enter, quickly penetrates into stone material capillary, carries out repairing and reinforcement；It is eventually adding film for additive and protective agent each component is anchored at into stone surface, it is dehydrated to form the stable chemistry key connection of-Si-O-Si- by silanol, it with polyurethane end group cocondensation, and introduces cagelike structure and improves the mechanical performance of glue film, and there is preferable wear-resisting property after making film forming.The present invention solves the problems, such as to be difficult to after current stone protectant protective film is damaged repair, protection effect is poor.
Description
Technical field
The present invention relates to stone protector fields more particularly to a kind of stone protectant and preparation method thereof.
Background technique
Stone material is constantly subjected to liking and paying attention to for people as a kind of important building decoration materials.From the Dark Ages
Splendid palace nowhere loses the trace of stone material to modern cloud-kissing mansion.On the one hand since stone material is with very high
Intensity and good physicochemical property, be widely used in building every field；Another aspect stone material has beautiful colorful color
The texture that the mystery that reconciles changes, is also able to satisfy the esthetic requirement of people in appearance.The surface of stone material can be divided into facet and thick
Grain surface, but because stone material be made of several mineral materials and have many holes, easily with other chemical reactions, nothing
By being that any surface all can be contaminated and corrode.In recent years, with the rapid development of industry, stone material is invaded in environmental pollution
Lose increasingly severe, the appearance of the stone material of serious shadow.The mankind gradually appreciate the significance of stone care.It is thought that very
More methods protect stone material damage, and to coat curing agent then in stone surface be the most widely used side in stone care field
Method.Stone care agent significantly improves the appearance of ornament materials, has important role in stone care field.Stone surface is anti-
There are many type for protecting agent, and classification is not quite similar, and can be divided by material property: inorganic surfaces protective agent and organic surfacecti proteon
Agent；It can be divided into according to protection method: semipermanent protection and permanent protection；Can be divided by mechanism of action: surface filming type and
Permeable crystallization type can be divided by purposes: surface-protective agent, bottom surface protective agent etc..Stone protectant experienced from nature material to
Synthetic material, from single to complicated process.First generation protective agent is vegetable material protective agent, with natural resin, natural gum
Deng based on, second generation protective agent is hard wax or wax liquor, these are all initial stage protective agents, and protection effect is poor, can only be played interim
Property protection effect, be born third generation impermeability protective agent and forth generation organosilicon permeability protective agent later, wherein having
Machine silicon waterproofing agent is the optimal a kind of stone protectant of current protection effect as a kind of vapor-permeable type protective agent.Organosilicon protection
In addition to infiltrating through stone material surface layer, superficial layer, very thin film layer (there are about 3 μ m-thicks) is also uniform-distribution with some ventilative the film layer of agent
The diameter in hole, these air holes is smaller than hydrone, bigger than water vapour molecule diameter.So when in the stone decoration face or back side
Moisture content is generated, because temperature increases, pressure increases, in stone material and stone material bottom surface moisture content can become moisture-vapour molecule, from organosilicon
It is released in hole, and since the hole on organic silicon thin layer is less than outside water molecule, and then outside water and aqueous dirt
Object just can not be into inside people's stone material, to achieve the purpose that waterproof, antifouling, grease proofing.Such as number of patent application
CN200910032710.1 disclose it is a kind of using methyl silicon sodium alcoholate as the water-based organic silicon waterproof agent of primary raw material, be suitable for it is porous
The water-proofing treatment of structure stone material can effectively improve stone material hydrophobic performance, and for another example number of patent application CN201110001005.2 is disclosed
A kind of fluorine-containing organic silicon stone anti-fouling agent after handling stone material using the anti-fouling agent, can make stone material that there is good surface water to connect
Feeler, anti-inkiness, the non-discolouring property of permeability and surface.However, being applied although organosilicon protective agent hydrophobicity is preferable
Once the protective agent film breakage for overlaying on stone surface will be difficult to repair, and can stone surface formed hole shape corrosion, not only without
Method protects stone material, also will affect the beauty of stone material.
Summary of the invention
The technical problems to be solved by the invention: for current stone protectant protective film it is damaged after be difficult to repair, protect
The problem of effect difference provides a kind of stone protectant and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of stone protectant, including reinforcement protection agent, additive of self-rehabilitation, osmotically active agent, film for additive；
The reinforcement protection agent the preparation method comprises the following steps: take calcium oxide 2 ~ 5:20 in mass ratio ~ 40 be added ethylene glycol, in 60 ~ 70 DEG C
It is stirred, obtains mixed liquor a, take phosphorus pentoxide 1 ~ 4:30 in mass ratio ~ 40 that dehydrated alcohol is added, add phosphorus pentoxide
The ethyl orthosilicate that 2 ~ 5 times of quality is stirred in 30 ~ 40 DEG C, obtains mixed liquor b, take mixed liquor a 3 ~ 5:2 in mass ratio ~ 7:1 ~
3 are added mixed liquor b, dimethyl silicone polymer, add the dibutyl tin dilaurate of mixed liquor a mass 1 ~ 4%, and ultrasound is stood
3 ~ 7 days, precipitating is taken to wash through deionized water, it is dry, dried object is obtained, takes dried object to keep the temperature in 700 ~ 800 DEG C, ground
200 meshes collect sieving particle to get reinforcement protection agent.
The additive of self-rehabilitation the preparation method comprises the following steps:
(1) according to the mass fraction, 40 ~ 50 parts of poly glycol monomethyl ethers, 1 ~ 3 part of N- methylol phthalimide, 2 ~ 5 parts of triphenyls are taken
Phosphine, 50 ~ 100 parts of methylene chloride mixing, are passed through nitrogen protection, are stirred in 20 ~ 25 DEG C, obtain mixture, take mixture by matter
Amount than 80 ~ 100:1 ~ 3 be added diisopropyl azodiformate, be stirred in 20 ~ 25 DEG C, obtain mixture a, take mixture a by
Ether is added in 3 ~ 7:10 of mass ratio ~ 20, is stirred in 0 ~ 4 DEG C, filters, filter cake is taken to wash through ether, dry, obtains dried object；
(2) it takes dried object 1 ~ 3:10 in mass ratio ~ 30 that methylene chloride is added, is stirred in 0 ~ 4 DEG C, addition dried object quality 2 ~
5 times of hydrazine hydrochloride adds the sodium hydroxide of dried object quality 10 ~ 20%, is stirred in 20 ~ 25 DEG C, and filtering takes filtrate to pass through
Saturated common salt water washing is stood, and takes subnatant rotary evaporation, is collected rotary evaporation residue, is taken rotary evaporation residue by matter
Ether is added than 2 ~ 5:40 ~ 50 in amount, stands, and filtering takes filter residue and drying to get additive of self-rehabilitation.
The osmotically active agent the preparation method comprises the following steps: to take decyl polyoxyethylene ether 1 ~ 3:3 in mass ratio ~ 5 that activity is added former
Material mixing, obtains mixture b, takes mixture b 2 ~ 5:10 in mass ratio ~ 20 that tetrahydrofuran is added, and it is mixed to be warming up to 120 ~ 130 DEG C of stirrings
It closes, filtering takes filtrate decompression to distill to get osmotically active agent.
The activated feedstock are as follows: take N, N- dimethyl urea 5 ~ 10:2 in mass ratio ~ 5:1 ~ 3 that carbonyl diamide urea, amino is added
Urea mixing to get.
The film for additive the preparation method comprises the following steps:
S1. it takes dihydromethyl propionic acid 2 ~ 5:10 in mass ratio ~ 40 that tetrahydrofuran is added, is passed through nitrogen protection, is warming up to 70 ~ 80
DEG C, the reactivity agent that tetrahydrofuran 30 ~ 40% is added is stirred, and adds 4,4-, bis- ring of tetrahydrofuran quality 20 ~ 30%
Hexyl methane diisocyanate is stirred in 70 ~ 80 DEG C, obtains stirring mixture, takes stirring mixture in mass ratio 80 ~ 100:
1 ~ 3 is added dibutyl tin dilaurate, keeps the temperature in 70 ~ 80 DEG C, must stir mixture a；
S2. take chain extension additive 1 ~ 3:20 in mass ratio ~ 30 be added tetrahydrofuran mixing, obtain mixed liquor, take stirring mixture a by
Mixed liquor is added in 60 ~ 90:3 of mass ratio ~ 8, is stirred in 70 ~ 80 DEG C, must stir mixture b, takes stirring mixture b by quality
Than 40 ~ 60:1 ~ 4:30 ~ 50 be added triethylamine, tetrahydrofuran, be stirred in 40 ~ 50 DEG C, obtain mixed liquor c, take mixed liquor c by
Silane activating agent is added in 10 ~ 30:2 of mass ratio ~ 5, is stirred in 20 ~ 30 DEG C, is evaporated under reduced pressure to get film for additive.
Reactivity agent in the step S1 are as follows: take polycarbonate glycol, polyadipate -1,4- butanediol ester, poly- four
Any one in hydrogen furans ether dihydric alcohol, polyethylene glycol adipate to get.
Chain extension additive in the step S2 are as follows: take 1,4- butanediol 3 ~ 7:2 in mass ratio ~ 5 that 2,2- dihydroxy first is added
Base butanol mixing to get.
Silane activating agent in the step S2 are as follows: according to the mass fraction, take 3 ~ 9 parts of aminoethylaminopropyl poly dimethyl silicon
Oxygen alkane, 2 ~ 5 parts of gamma-aminopropyl-triethoxy-silanes, the mixing of 10 ~ 15 parts of aminopropyl isobutyl group silsesquioxanes to get.
The preparation method includes the following steps: that being derived from repair additive 10 ~ 15:1 in mass ratio ~ 3:80 ~ 100 is added crosslinking
Activating agent, deionized water are stirred in 20 ~ 25 DEG C, must stir mixture c, according to the mass fraction, are taken 10 ~ 20 parts to reinforce and are prevented
Protect agent, 20 ~ 40 parts of stirring mixture c, 5 ~ 10 parts of osmotically active agent, 70 ~ 100 parts of film for additive, 0.1 ~ 0.5 part of potassium peroxydisulfate
Mixing, obtains matrix object, takes matrix object 100 ~ 150:1 in mass ratio ~ 3:5 ~ 10 that tetramethylethylenediamine, deionized water is added, is passed through
Nitrogen protection is stirred in 40 ~ 60 DEG C to get stone protectant.
The cure activating ingredient are as follows: according to the mass fraction, take 3 ~ 9 parts of N,N-DMAAs, 2 ~ 5 parts of diacetones third
Acrylamide, the mixing of 3 ~ 6 parts of n-isopropyl acrylamide to get.
The present invention is compared with other methods, and advantageous effects are:
(1) reinforcement protection agent prepared by the present invention be using the ethanol solution of the ethylene glycol solution of calcium oxide and phosphorus pentoxide as
Presoma carries out mineralising induction using the activity hydroxy of stone surface, accelerates nucleation rate and make oriented crystal growth, to stone material
Surface layer is reinforced, and introduces ethyl orthosilicate and dimethyl silicone polymer in the process, forms colloidal sol induction calcium carbonate in stone material
It is grown in capillary porosity, has good compatibility and binding force with former stone material, carry out the hardening reinforcement protection of stone material；
(2) additive of self-rehabilitation prepared by the present invention is utilized using poly glycol monomethyl ether, N- methylol phthalimide as raw material
N- methylol phthalimide is etherified with alcoholic extract hydroxyl group, then carries out hydrazinolysis reaction through hydrazine hydrochloride, by the end of additive of self-rehabilitation
It is modified into oxygen amido, cure activating ingredient formation oxime key is added and is introduced into stone protectant, is formed on protective layer surface layer from group
Dress, is fixed on polymer network by reversible oxime key, not only introduces the energy dissipation mechanism of micella, while can make to polymerize
Object network can reconnect by the reversible exchange reaction of oxime key after disruption, and the mutual synergistic effect of the two obtains power
Learn the double excellent polyalcohol hydrogels of performance and self-healing performance, under the conditions of stone material is by acid etching, acidified easy formation oxime key and
It is self-assembly of three-dimensional cross-linked reticular structure, shock resistance and tensile property are improved, and are being caused glue film damaged by external force
When, oxime key fracture, micella scatters, and is handed over again using the reversibility of oxime key and the macromolecular chain formation in protection film forming layer at this time
Connection healing, re-forms restoration and protection layer, carries out the selfreparing of stone surface；
(3) osmotically active agent prepared by the present invention is with decyl polyoxyethylene ether and N, and N- dimethyl urea presses, carbonyl diamide urea etc.
Carbamate sealing end is carried out to the modified-reaction of polyethers end position hydroxyl for raw material, urea groups is introduced and improves protective agent in stone material
Wettability of the surface, the surface tension contacted by reducing protective agent with stone surface, so that protective agent can enter quick infiltration
Stone material capillary carries out repairing and reinforcement, and sprawls in stone surface, forms protective layer；
(4) film for additive prepared by the present invention is different with reactivity agent, dihydromethyl propionic acid, 4,4- dicyclohexyl methyl hydride two
Cyanate is primary raw material, forms the film forming basement membrane of polyurethane-type through chain extension, introduces aminoethylaminopropyl during preparation
Dimethyl silicone polymer, gamma-aminopropyl-triethoxy-silane, aminopropyl isobutyl group silsesquioxane, can be from shampoo in water phase
Solution forms silanol structure, keeps stability, protective agent each component is anchored at stone surface, is dehydrated to form-Si- by silanol
O-Si- stable chemistry key connection, and polyurethane end group cocondensation, using low polar silicon oxygen bond segment enable protective agent with
Crosslinking is formed between stone material matrix, protective agent each component, increases the compatibility between component, and the adhesive force after improving film forming draws
The aminopropyl isobutyl group silsesquioxane entered is reacted with the formation of polyurethane end group, and cagelike structure improves the mechanicalness of glue film
Can, and there is preferable wear-resisting property after making film forming, preferably stone surface can be protected.
Specific embodiment
Reinforcement protection agent the preparation method comprises the following steps: take calcium oxide 2 ~ 5:20 in mass ratio ~ 40 be added ethylene glycol, in 60 ~ 70 DEG C
It is stirred 30 ~ 50min, obtains mixed liquor a, takes phosphorus pentoxide 1 ~ 4:30 in mass ratio ~ 40 that dehydrated alcohol is added, adds five
The ethyl orthosilicate for aoxidizing 2 ~ 5 times of two phosphorus quality is stirred 20 ~ 50min in 30 ~ 40 DEG C, obtains mixed liquor b, take mixed liquor a by
Mixed liquor b, dimethyl silicone polymer is added in 3 ~ 5:2 of mass ratio ~ 7:1 ~ 3, adds the tin dilaurate two of mixed liquor a mass 1 ~ 4%
Butyl tin, 10 ~ 20min of ultrasound stand 3 ~ 7 days, and precipitating is taken to wash through deionized water, dry, obtain dried object, take dried object in
700 ~ 800 DEG C of 1 ~ 3h of heat preservation ground 200 meshes, collected sieving particle to get reinforcement protection agent.
Additive of self-rehabilitation the preparation method comprises the following steps:
(1) according to the mass fraction, 40 ~ 50 parts of poly glycol monomethyl ethers, 1 ~ 3 part of N- methylol phthalimide, 2 ~ 5 parts of triphenyls are taken
Phosphine, 50 ~ 100 parts of methylene chloride mixing, are passed through nitrogen protection, are stirred 10 ~ 20min in 20 ~ 25 DEG C, obtain mixture, take mixed
It closes object 80 ~ 100:1 in mass ratio ~ 3 and diisopropyl azodiformate is added, it is stirred 18 in 20 ~ 25 DEG C ~ for 24 hours, obtain mixture
A takes mixture a 3 ~ 7:10 in mass ratio ~ 20 that ether is added, is stirred 20 ~ 30min in 0 ~ 4 DEG C, filters, takes filter cake through second
Ether washing, it is dry, obtain dried object；
(2) it takes dried object 1 ~ 3:10 in mass ratio ~ 30 that methylene chloride is added, 20 ~ 30min is stirred in 0 ~ 4 DEG C, drying is added
The hydrazine hydrochloride that 2 ~ 5 times of amount of substance adds the sodium hydroxide of dried object quality 10 ~ 20%, is stirred 10 ~ 12h in 20 ~ 25 DEG C,
Filtering takes filtrate through saturated common salt water washing, stands 20 ~ 30min, take subnatant rotary evaporation, collects rotary evaporation residue,
It takes rotary evaporation residue 2 ~ 5:40 in mass ratio ~ 50 that ether is added, stands 30 ~ 60min, filtering takes filter residue and drying to get certainly
Repair additive.
Activated feedstock are as follows: take N, it is mixed that carbonyl diamide urea, semicarbazides is added in N- dimethyl urea 5 ~ 10:2 in mass ratio ~ 5:1 ~ 3
Close to get.
Osmotically active agent mixes the preparation method comprises the following steps: taking decyl polyoxyethylene ether 1 ~ 3:3 in mass ratio ~ 5 that activated feedstock is added
Close, obtain mixture b, take mixture b 2 ~ 5:10 in mass ratio ~ 20 that tetrahydrofuran is added, be warming up to 120 ~ 130 DEG C be stirred 2 ~
5h, filtering, takes filtrate decompression to distill to get osmotically active agent.
Reactivity agent are as follows: take polycarbonate glycol, polyadipate -1,4- butanediol ester, polytetrahydrofuran ether dihydric alcohol,
Any one in polyethylene glycol adipate to get.
Chain extension additive are as follows: take 1,4-butanediol 3 ~ 7:2 in mass ratio ~ 5 that the mixing of 2,2- dihydroxymethyl butanol is added, i.e.,
?.
Silane activating agent are as follows: according to the mass fraction, take 3 ~ 9 parts of aminoethylaminopropyl dimethyl silicone polymers, 2 ~ 5 parts of γ-
Aminopropyl triethoxysilane, the mixing of 10 ~ 15 parts of aminopropyl isobutyl group silsesquioxanes to get.
Film for additive the preparation method comprises the following steps:
S1. it takes dihydromethyl propionic acid 2 ~ 5:10 in mass ratio ~ 40 that tetrahydrofuran is added, is passed through nitrogen protection, is warming up to 70 ~ 80
DEG C, the reactivity agent of tetrahydrofuran 30 ~ 40% is added, is stirred 20 ~ 40min, adds tetrahydrofuran quality 20 ~ 30%
4,4- dicyclohexyl methyl hydride diisocyanates are stirred 20 ~ 40min in 70 ~ 80 DEG C, obtain stirring mixture, take and be stirred
Dibutyl tin dilaurate, which is added, in object 80 ~ 100:1 in mass ratio ~ 3 must stir mixture a in 70 ~ 80 DEG C of 1 ~ 3h of heat preservation；
S2. take chain extension additive 1 ~ 3:20 in mass ratio ~ 30 be added tetrahydrofuran mixing, obtain mixed liquor, take stirring mixture a by
60 ~ 90:3 of mass ratio ~ 8 be added mixed liquor, be stirred 5 ~ 8h in 70 ~ 80 DEG C, must stir mixture b, take stir mixture b by
Triethylamine, tetrahydrofuran is added in 40 ~ 60:1 of mass ratio ~ 4:30 ~ 50, is stirred 20 ~ 50min in 40 ~ 50 DEG C, obtains mixed liquor c,
Take mixed liquor c 10 ~ 30:2 in mass ratio ~ 5 that silane activating agent is added, be stirred 1 ~ 3h in 20 ~ 30 DEG C, vacuum distillation to get
Film for additive.
Cure activating ingredient are as follows: according to the mass fraction, take 3 ~ 9 parts of N,N-DMAAs, 2 ~ 5 parts of diacetone acrylamide acyls
Amine, the mixing of 3 ~ 6 parts of n-isopropyl acrylamide to get.
A kind of preparation method of stone protectant, include the following steps: to be derived from repair additive 10 ~ 15:1 in mass ratio ~
Cure activating ingredient, deionized water is added in 3:80 ~ 100, is stirred 10 ~ 16h in 20 ~ 25 DEG C, mixture c must be stirred, by quality
Number meter takes 10 ~ 20 parts of reinforcement protection agent, 20 ~ 40 parts of stirring mixture c, 5 ~ 10 parts of osmotically active agent, 70 ~ 100 parts of film forming to add
Add agent, 0.1 ~ 0.5 part of potassium peroxydisulfate mixing, obtains matrix object, take matrix object 100 ~ 150:1 in mass ratio ~ 3:5 ~ 10 that tetramethyl is added
Base ethylenediamine, deionized water, are passed through nitrogen protection, it is stirred 18 in 40 ~ 60 DEG C ~ for 24 hours to get stone protectant.
Reinforcement protection agent the preparation method comprises the following steps: take calcium oxide 2:20 in mass ratio be added ethylene glycol, be stirred in 60 DEG C
30min obtains mixed liquor a, takes phosphorus pentoxide 1:30 in mass ratio that dehydrated alcohol is added, adds 2 times of phosphorus pentoxide quality
Ethyl orthosilicate, be stirred 20min in 30 DEG C, obtain mixed liquor b, take mixed liquor a 3:2:1 in mass ratio be added mixed liquor b,
Dimethyl silicone polymer, adds the dibutyl tin dilaurate of mixed liquor a mass 1%, and ultrasonic 10min stands 3 days, takes precipitating
It is washed through deionized water, it is dry, dried object is obtained, takes dried object in 700 DEG C of heat preservation 1h, ground 200 meshes, collect sieving
Particle is to get reinforcement protection agent.
Additive of self-rehabilitation the preparation method comprises the following steps:
(1) according to the mass fraction, 40 parts of poly glycol monomethyl ethers, 1 part of N- methylol phthalimide, 2 parts of triphenylphosphines, 50 parts are taken
Methylene chloride mixing, is passed through nitrogen protection, is stirred 10min in 20 DEG C, obtains mixture, mixture 80:1 in mass ratio is taken to add
Enter diisopropyl azodiformate, be stirred 18h in 20 DEG C, obtain mixture a, takes mixture a 3:10 in mass ratio that second is added
Ether is stirred 20min in 0 DEG C, and filtering takes filter cake to wash through ether, dry, obtains dried object；
(2) it takes dried object 1:10 in mass ratio that methylene chloride is added, 20min is stirred in 0 DEG C, be added 2 times of dried object quality
Hydrazine hydrochloride, add the sodium hydroxide of dried object quality 10%, be stirred 10h in 20 DEG C, filter, take filtrate through saturation eat
Salt water washing stands 20min, takes subnatant rotary evaporation, collects rotary evaporation residue, takes rotary evaporation residue by quality
Ether is added than 2:40, stands 30min, filtering takes filter residue and drying to get additive of self-rehabilitation.
Activated feedstock are as follows: take N, N- dimethyl urea 5:2:1 in mass ratio be added carbonyl diamide urea, semicarbazides mixing to get.
Mixing the preparation method comprises the following steps: taking decyl polyoxyethylene ether 1:3 in mass ratio that activated feedstock is added for osmotically active agent, obtains
Mixture b takes mixture b 2:10 in mass ratio that tetrahydrofuran is added, is warming up to 120 DEG C and is stirred 2h, filters, filtrate is taken to subtract
Pressure distillation is to get osmotically active agent.
Reactivity agent are as follows: take polycarbonate glycol.
Chain extension additive are as follows: take 1,4-butanediol 3:2 in mass ratio be added 2,2- dihydroxymethyl butanol mixing to get.
Silane activating agent are as follows: according to the mass fraction, take 3 parts of aminoethylaminopropyl dimethyl silicone polymers, 2 parts of γ-ammonia third
Ethyl triethoxy silicane alkane, the mixing of 10 parts of aminopropyl isobutyl group silsesquioxanes to get.
Film for additive the preparation method comprises the following steps:
S1. it takes dihydromethyl propionic acid 2:10 in mass ratio that tetrahydrofuran is added, is passed through nitrogen protection, be warming up to 70 DEG C, be added four
The reactivity agent of hydrogen furans 30%, is stirred 20min, adds 4, the 4- dicyclohexyl methyl hydride two of tetrahydrofuran quality 20%
Isocyanates is stirred 20min in 70 DEG C, obtains stirring mixture, takes stirring mixture 80:1 in mass ratio that two laurels are added
Sour dibutyl tin must stir mixture a in 70 DEG C of heat preservation 1h；
S2. it takes chain extension additive 1:20 in mass ratio that tetrahydrofuran mixing is added, obtains mixed liquor, take stirring mixture a by quality
Mixed liquor is added than 60:3, is stirred 5h in 70 DEG C, mixture b must be stirred, takes stirring mixture b 40:1:30 in mass ratio
Triethylamine, tetrahydrofuran is added, is stirred 20min in 40 DEG C, obtains mixed liquor c, takes mixed liquor c 10:2 in mass ratio that silicon is added
Alkane activating agent is stirred 1h in 20 DEG C, is evaporated under reduced pressure to get film for additive.
Cure activating ingredient are as follows: according to the mass fraction, take 3 parts of N,N-DMAAs, 2 parts of Diacetone Acrylamide, 3
The mixing of part n-isopropyl acrylamide to get.
A kind of preparation method of stone protectant includes the following steps: that being derived from repair additive 10:1:80 in mass ratio adds
Enter cure activating ingredient, deionized water, be stirred 10h in 20 DEG C, mixture c must be stirred, according to the mass fraction, takes 10 parts of reinforcings
Protective agent, 20 parts of stirring mixture c, 5 parts of osmotically active agent, 70 parts of film for additive, 0.1 part of potassium peroxydisulfate mixing, obtain matrix
Object takes matrix object 100:1:5 in mass ratio that tetramethylethylenediamine, deionized water is added, is passed through nitrogen protection, mixed in 40 DEG C of stirrings
18h is closed to get stone protectant.
Reinforcement protection agent the preparation method comprises the following steps: take calcium oxide 5:40 in mass ratio be added ethylene glycol, be stirred in 70 DEG C
50min obtains mixed liquor a, takes phosphorus pentoxide 4:40 in mass ratio that dehydrated alcohol is added, adds 5 times of phosphorus pentoxide quality
Ethyl orthosilicate, be stirred 50min in 40 DEG C, obtain mixed liquor b, take mixed liquor a 5:7:3 in mass ratio be added mixed liquor b,
Dimethyl silicone polymer, adds the dibutyl tin dilaurate of mixed liquor a mass 4%, and ultrasonic 20min stands 7 days, takes precipitating
It is washed through deionized water, it is dry, dried object is obtained, takes dried object in 800 DEG C of heat preservation 3h, ground 200 meshes, collect sieving
Particle is to get reinforcement protection agent.
Additive of self-rehabilitation the preparation method comprises the following steps:
(1) according to the mass fraction, 50 parts of poly glycol monomethyl ethers, 3 parts of N- methylol phthalimides, 5 parts of triphenylphosphines, 100 are taken
Part methylene chloride mixing, is passed through nitrogen protection, is stirred 20min in 25 DEG C, obtains mixture, take mixture in mass ratio 100:
3 are added diisopropyl azodiformate, are stirred for 24 hours in 25 DEG C, obtain mixture a, and mixture a 7:20 in mass ratio is taken to be added
Ether is stirred 30min in 4 DEG C, and filtering takes filter cake to wash through ether, dry, obtains dried object；
(2) it takes dried object 3:30 in mass ratio that methylene chloride is added, 30min is stirred in 4 DEG C, be added 5 times of dried object quality
Hydrazine hydrochloride, add the sodium hydroxide of dried object quality 20%, be stirred 12h in 25 DEG C, filter, take filtrate through saturation eat
Salt water washing stands 30min, takes subnatant rotary evaporation, collects rotary evaporation residue, takes rotary evaporation residue by quality
Ether is added than 5:50, stands 60min, filtering takes filter residue and drying to get additive of self-rehabilitation.
Activated feedstock are as follows: take N, N- dimethyl urea 10:5:3 in mass ratio that carbonyl diamide urea, semicarbazides mixing is added, i.e.,
?.
Mixing the preparation method comprises the following steps: taking decyl polyoxyethylene ether 3:5 in mass ratio that activated feedstock is added for osmotically active agent, obtains
Mixture b takes mixture b 5:20 in mass ratio that tetrahydrofuran is added, is warming up to 130 DEG C and is stirred 5h, filters, filtrate is taken to subtract
Pressure distillation is to get osmotically active agent.
Reactivity agent are as follows: take polyadipate -1,4- butanediol ester.
Chain extension additive are as follows: take 1,4-butanediol 7:5 in mass ratio be added 2,2- dihydroxymethyl butanol mixing to get.
Silane activating agent are as follows: according to the mass fraction, take 9 parts of aminoethylaminopropyl dimethyl silicone polymers, 5 parts of γ-ammonia third
Ethyl triethoxy silicane alkane, the mixing of 15 parts of aminopropyl isobutyl group silsesquioxanes to get.
Film for additive the preparation method comprises the following steps:
S1. it takes dihydromethyl propionic acid 5:40 in mass ratio that tetrahydrofuran is added, is passed through nitrogen protection, be warming up to 80 DEG C, be added four
The reactivity agent of hydrogen furans 40%, is stirred 40min, adds 4, the 4- dicyclohexyl methyl hydride two of tetrahydrofuran quality 30%
Isocyanates is stirred 40min in 80 DEG C, obtains stirring mixture, takes stirring mixture 100:3 in mass ratio that two laurels are added
Sour dibutyl tin must stir mixture a in 80 DEG C of heat preservation 3h；
S2. it takes chain extension additive 3:30 in mass ratio that tetrahydrofuran mixing is added, obtains mixed liquor, take stirring mixture a by quality
Mixed liquor is added than 90:8, is stirred 8h in 80 DEG C, mixture b must be stirred, takes stirring mixture b 60:4:50 in mass ratio
Triethylamine, tetrahydrofuran is added, is stirred 50min in 50 DEG C, obtains mixed liquor c, takes mixed liquor c 30:5 in mass ratio that silicon is added
Alkane activating agent is stirred 3h in 30 DEG C, is evaporated under reduced pressure to get film for additive.
Cure activating ingredient are as follows: according to the mass fraction, take 9 parts of N,N-DMAAs, 5 parts of Diacetone Acrylamide, 6
The mixing of part n-isopropyl acrylamide to get.
A kind of preparation method of stone protectant includes the following steps: to be derived from repair additive 15:3:100 in mass ratio
Cure activating ingredient, deionized water is added, is stirred 16h in 25 DEG C, mixture c must be stirred, according to the mass fraction, takes 20 parts to add
Gu protective agent, 40 parts of stirring mixture c, 10 parts of osmotically active agent, 100 parts of film for additive, 0.5 part of potassium peroxydisulfate mixing, obtain
Matrix object takes matrix object 150:3:10 in mass ratio that tetramethylethylenediamine, deionized water is added, nitrogen protection is passed through, in 60 DEG C
It is stirred for 24 hours to get stone protectant.
Reinforcement protection agent the preparation method comprises the following steps: take calcium oxide 3:30 in mass ratio be added ethylene glycol, be stirred in 65 DEG C
40min obtains mixed liquor a, takes phosphorus pentoxide 2:35 in mass ratio that dehydrated alcohol is added, adds 3 times of phosphorus pentoxide quality
Ethyl orthosilicate, be stirred 40min in 35 DEG C, obtain mixed liquor b, take mixed liquor a 4:5:2 in mass ratio be added mixed liquor b,
Dimethyl silicone polymer, adds the dibutyl tin dilaurate of mixed liquor a mass 3%, and ultrasonic 15min stands 5 days, takes precipitating
It is washed through deionized water, it is dry, dried object is obtained, takes dried object in 750 DEG C of heat preservation 2h, ground 200 meshes, collect sieving
Particle is to get reinforcement protection agent.
Additive of self-rehabilitation the preparation method comprises the following steps:
(1) according to the mass fraction, 45 parts of poly glycol monomethyl ethers, 2 parts of N- methylol phthalimides, 3 parts of triphenylphosphines, 70 parts are taken
Methylene chloride mixing, is passed through nitrogen protection, is stirred 15min in 22 DEG C, obtains mixture, mixture 90:2 in mass ratio is taken to add
Enter diisopropyl azodiformate, be stirred 20h in 23 DEG C, obtain mixture a, takes mixture a 5:15 in mass ratio that second is added
Ether is stirred 25min in 3 DEG C, and filtering takes filter cake to wash through ether, dry, obtains dried object；
(2) it takes dried object 2:20 in mass ratio that methylene chloride is added, 25min is stirred in 3 DEG C, be added 3 times of dried object quality
Hydrazine hydrochloride, add the sodium hydroxide of dried object quality 15%, be stirred 11h in 23 DEG C, filter, take filtrate through saturation eat
Salt water washing stands 25min, takes subnatant rotary evaporation, collects rotary evaporation residue, takes rotary evaporation residue by quality
Ether is added than 3:45, stands 50min, filtering takes filter residue and drying to get additive of self-rehabilitation.
Activated feedstock are as follows: take N, N- dimethyl urea 7:3:2 in mass ratio be added carbonyl diamide urea, semicarbazides mixing to get.
Mixing the preparation method comprises the following steps: taking decyl polyoxyethylene ether 2:4 in mass ratio that activated feedstock is added for osmotically active agent, obtains
Mixture b takes mixture b 3:15 in mass ratio that tetrahydrofuran is added, is warming up to 125 DEG C and is stirred 3h, filters, filtrate is taken to subtract
Pressure distillation is to get osmotically active agent.
Reactivity agent are as follows: take polytetrahydrofuran ether dihydric alcohol.
Chain extension additive are as follows: take 1,4-butanediol 5:3 in mass ratio be added 2,2- dihydroxymethyl butanol mixing to get.
Silane activating agent are as follows: according to the mass fraction, take 6 parts of aminoethylaminopropyl dimethyl silicone polymers, 3 parts of γ-ammonia third
Ethyl triethoxy silicane alkane, the mixing of 12 parts of aminopropyl isobutyl group silsesquioxanes to get.
Film for additive the preparation method comprises the following steps:
S1. it takes dihydromethyl propionic acid 3:30 in mass ratio that tetrahydrofuran is added, is passed through nitrogen protection, be warming up to 75 DEG C, be added four
The reactivity agent of hydrogen furans 35%, is stirred 30min, adds 4, the 4- dicyclohexyl methyl hydride two of tetrahydrofuran quality 25%
Isocyanates is stirred 30min in 75 DEG C, obtains stirring mixture, takes stirring mixture 90:2 in mass ratio that two laurels are added
Sour dibutyl tin must stir mixture a in 75 DEG C of heat preservation 2h；
S2. it takes chain extension additive 2:25 in mass ratio that tetrahydrofuran mixing is added, obtains mixed liquor, take stirring mixture a by quality
Mixed liquor is added than 70:5, is stirred 6h in 75 DEG C, mixture b must be stirred, takes stirring mixture b 50:3:40 in mass ratio
Triethylamine, tetrahydrofuran is added, is stirred 30min in 45 DEG C, obtains mixed liquor c, takes mixed liquor c 20:3 in mass ratio that silicon is added
Alkane activating agent is stirred 2h in 25 DEG C, is evaporated under reduced pressure to get film for additive.
Cure activating ingredient are as follows: according to the mass fraction, take 5 parts of N,N-DMAAs, 3 parts of Diacetone Acrylamide, 5
The mixing of part n-isopropyl acrylamide to get.
A kind of preparation method of stone protectant includes the following steps: that being derived from repair additive 13:2:90 in mass ratio adds
Enter cure activating ingredient, deionized water, be stirred 13h in 21 DEG C, mixture c must be stirred, according to the mass fraction, takes 15 parts of reinforcings
Protective agent, 30 parts of stirring mixture c, 7 parts of osmotically active agent, 80 parts of film for additive, 0.3 part of potassium peroxydisulfate mixing, obtain matrix
Object takes matrix object 120:2:7 in mass ratio that tetramethylethylenediamine, deionized water is added, is passed through nitrogen protection, mixed in 50 DEG C of stirrings
20h is closed to get stone protectant.
Comparative example 1: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking reinforcement protection agent.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking additive of self-rehabilitation.
Comparative example 3: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking osmotically active agent.
Comparative example 4: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking film for additive.
Comparative example 5: the stone protectant of company, Fujian Province production.
By above-described embodiment and the stone protectant of comparative example preparation according to JC/T973-2005 " architectural decoration natural stone
Material protective agent " standard detection protective performance, obtain that the results are shown in Table 1.
Table 1:
| Detection project | Acid resistance/% | Alkali resistance/% | UV resistant/% | Resistance to soiling/grade | Stability |
| Embodiment 1 | 65 | 60 | 61 | 0 | Without layering, without precipitating |
| Embodiment 2 | 68 | 62 | 63 | 0 | Without layering, without precipitating |
| Embodiment 3 | 63 | 61 | 60 | 0 | Without layering, without precipitating |
| Comparative example 1 | 59 | 57 | 58 | 1 | Without being layered, have precipitating |
| Comparative example 2 | 47 | 53 | 57 | 1 | There is layering, without precipitating |
| Comparative example 3 | 53 | 51 | 46 | 1 | Without being layered, have precipitating |
| Comparative example 4 | 56 | 41 | 51 | 1 | There is layering, without precipitating |
| Comparative example 5 | 40 | 40 | 42 | 2 | There is layering, have precipitating |
In summary, stone protectant effect of the invention is more preferable as can be seen from Table 1, is worth of widely use, it is described above only
For preferred mode of the invention, it is not intended to limit the invention, it is all within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of stone protectant, which is characterized in that add including reinforcement protection agent, additive of self-rehabilitation, osmotically active agent, film forming
Add agent；
The reinforcement protection agent the preparation method comprises the following steps: take calcium oxide 2 ~ 5:20 in mass ratio ~ 40 be added ethylene glycol, in 60 ~ 70 DEG C
It is stirred, obtains mixed liquor a, take phosphorus pentoxide 1 ~ 4:30 in mass ratio ~ 40 that dehydrated alcohol is added, add phosphorus pentoxide
The ethyl orthosilicate that 2 ~ 5 times of quality is stirred in 30 ~ 40 DEG C, obtains mixed liquor b, take mixed liquor a 3 ~ 5:2 in mass ratio ~ 7:1 ~
3 are added mixed liquor b, dimethyl silicone polymer, add the dibutyl tin dilaurate of mixed liquor a mass 1 ~ 4%, and ultrasound is stood
3 ~ 7 days, precipitating is taken to wash through deionized water, it is dry, dried object is obtained, takes dried object to keep the temperature in 700 ~ 800 DEG C, ground
200 meshes collect sieving particle to get reinforcement protection agent.
2. stone protectant according to claim 1, which is characterized in that the additive of self-rehabilitation the preparation method comprises the following steps:
(1) according to the mass fraction, 40 ~ 50 parts of poly glycol monomethyl ethers, 1 ~ 3 part of N- methylol phthalimide, 2 ~ 5 parts of triphenyls are taken
Phosphine, 50 ~ 100 parts of methylene chloride mixing, are passed through nitrogen protection, are stirred in 20 ~ 25 DEG C, obtain mixture, take mixture by matter
Amount than 80 ~ 100:1 ~ 3 be added diisopropyl azodiformate, be stirred in 20 ~ 25 DEG C, obtain mixture a, take mixture a by
Ether is added in 3 ~ 7:10 of mass ratio ~ 20, is stirred in 0 ~ 4 DEG C, filters, filter cake is taken to wash through ether, dry, obtains dried object；
(2) it takes dried object 1 ~ 3:10 in mass ratio ~ 30 that methylene chloride is added, is stirred in 0 ~ 4 DEG C, addition dried object quality 2 ~
5 times of hydrazine hydrochloride adds the sodium hydroxide of dried object quality 10 ~ 20%, is stirred in 20 ~ 25 DEG C, and filtering takes filtrate to pass through
Saturated common salt water washing is stood, and takes subnatant rotary evaporation, is collected rotary evaporation residue, is taken rotary evaporation residue by matter
Ether is added than 2 ~ 5:40 ~ 50 in amount, stands, and filtering takes filter residue and drying to get additive of self-rehabilitation.
3. stone protectant according to claim 1, which is characterized in that the osmotically active agent the preparation method comprises the following steps: taking
Activated feedstock mixing is added in decyl polyoxyethylene ether 1 ~ 3:3 in mass ratio ~ 5, obtains mixture b, takes mixture b in mass ratio 2 ~ 5:
10 ~ 20 are added tetrahydrofuran, are warming up to 120 ~ 130 DEG C and are stirred, and filter, take filtrate decompression to distill to get osmotically active agent.
4. stone protectant according to claim 3, which is characterized in that the activated feedstock are as follows: take N, N- dimethyl urea
5 ~ 10:2 in mass ratio ~ 5:1 ~ 3 be added carbonyl diamide urea, semicarbazides mixing to get.
5. stone protectant according to claim 1, which is characterized in that the film for additive the preparation method comprises the following steps:
S1. it takes dihydromethyl propionic acid 2 ~ 5:10 in mass ratio ~ 40 that tetrahydrofuran is added, is passed through nitrogen protection, is warming up to 70 ~ 80
DEG C, the reactivity agent that tetrahydrofuran 30 ~ 40% is added is stirred, and adds 4,4-, bis- ring of tetrahydrofuran quality 20 ~ 30%
Hexyl methane diisocyanate is stirred in 70 ~ 80 DEG C, obtains stirring mixture, takes stirring mixture in mass ratio 80 ~ 100:
1 ~ 3 is added dibutyl tin dilaurate, keeps the temperature in 70 ~ 80 DEG C, must stir mixture a；
S2. take chain extension additive 1 ~ 3:20 in mass ratio ~ 30 be added tetrahydrofuran mixing, obtain mixed liquor, take stirring mixture a by
Mixed liquor is added in 60 ~ 90:3 of mass ratio ~ 8, is stirred in 70 ~ 80 DEG C, must stir mixture b, takes stirring mixture b by quality
Than 40 ~ 60:1 ~ 4:30 ~ 50 be added triethylamine, tetrahydrofuran, be stirred in 40 ~ 50 DEG C, obtain mixed liquor c, take mixed liquor c by
Silane activating agent is added in 10 ~ 30:2 of mass ratio ~ 5, is stirred in 20 ~ 30 DEG C, is evaporated under reduced pressure to get film for additive.
6. stone protectant according to claim 5, which is characterized in that the reactivity agent in the step S1 are as follows: take
It is polycarbonate glycol, polyadipate -1,4- butanediol ester, polytetrahydrofuran ether dihydric alcohol, any in polyethylene glycol adipate
One kind to get.
7. stone protectant according to claim 5, which is characterized in that the chain extension additive in the step S2 are as follows: take
1,4-butanediol 3 ~ 7:2 in mass ratio ~ 5 be added 2,2- dihydroxymethyl butanol mixing to get.
8. stone protectant according to claim 5, which is characterized in that the silane activating agent in the step S2 are as follows: press
Mass fraction meter takes 3 ~ 9 parts of aminoethylaminopropyl dimethyl silicone polymers, 2 ~ 5 parts of gamma-aminopropyl-triethoxy-silanes, 10 ~ 15
The mixing of part aminopropyl isobutyl group silsesquioxane to get.
9. a kind of preparation method of the stone protectant as described in claim 1 ~ 8 any one, which is characterized in that the preparation side
Method includes the following steps: that being derived from repair additive 10 ~ 15:1 in mass ratio ~ 3:80 ~ 100 is added cure activating ingredient, deionized water,
It is stirred in 20 ~ 25 DEG C, mixture c must be stirred, according to the mass fraction, take 10 ~ 20 parts of reinforcement protection agent, 20 ~ 40 parts of stirrings
Mixture c, 5 ~ 10 parts of osmotically active agent, 70 ~ 100 parts of film for additive, 0.1 ~ 0.5 part of potassium peroxydisulfate mixing, obtain matrix object, take
Tetramethylethylenediamine, deionized water is added in matrix object 100 ~ 150:1 in mass ratio ~ 3:5 ~ 10, nitrogen protection is passed through, in 40 ~ 60
It DEG C is stirred to get stone protectant.
10. the preparation method of stone protectant according to claim 9, which is characterized in that the cure activating ingredient are as follows: press
Mass fraction meter takes 3 ~ 9 parts of N,N-DMAAs, 2 ~ 5 parts of Diacetone Acrylamide, 3 ~ 6 parts of N- isopropyl acrylamides
Amine mixing to get.
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| CN201910059831.9A CN109777281A (en) | 2019-01-22 | 2019-01-22 | A kind of stone protectant and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200134836A (en) * | 2019-05-24 | 2020-12-02 | 한국생산기술연구원 | Polyurethane based self-healing clear coat composition and manufacturing method thereof |
| CN112592205A (en) * | 2020-12-18 | 2021-04-02 | 杨华 | Concrete freeze-thaw resisting composite protective agent and preparation method thereof |
| CN115124923A (en) * | 2021-08-26 | 2022-09-30 | 上海佐航新材料科技有限公司 | Environment-friendly stone protective agent and preparation method thereof |
-
2019
- 2019-01-22 CN CN201910059831.9A patent/CN109777281A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200134836A (en) * | 2019-05-24 | 2020-12-02 | 한국생산기술연구원 | Polyurethane based self-healing clear coat composition and manufacturing method thereof |
| KR102218035B1 (en) * | 2019-05-24 | 2021-02-19 | 한국생산기술연구원 | Polyurethane based self-healing clear coat composition and manufacturing method thereof |
| CN112592205A (en) * | 2020-12-18 | 2021-04-02 | 杨华 | Concrete freeze-thaw resisting composite protective agent and preparation method thereof |
| CN115124923A (en) * | 2021-08-26 | 2022-09-30 | 上海佐航新材料科技有限公司 | Environment-friendly stone protective agent and preparation method thereof |
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