CN104844759A - Polymer containing a carbamoyl group and preparation method thereof - Google Patents

Polymer containing a carbamoyl group and preparation method thereof Download PDF

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CN104844759A
CN104844759A CN201510190925.1A CN201510190925A CN104844759A CN 104844759 A CN104844759 A CN 104844759A CN 201510190925 A CN201510190925 A CN 201510190925A CN 104844759 A CN104844759 A CN 104844759A
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ocf
monomer
nhcooch
based polyalcohol
cooch
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CN104844759B (en
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裴金东
李建
杨建荣
周强
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Zhejiang Chuangfu high tech new material Co.,Ltd.
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QUZHOU FLUORIDE AND SILICON RESEARCH INSTITUTES
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Abstract

The invention discloses a polymer containing a carbamoyl group. The polymer is composed of, by weight, 100-140 parts of a fluorine-containing monomer, 15-100 parts of a non-fluorine-containing comonomer, 0-5 parts of a functional additive, 0-20 parts of a modifier, 400-600 parts of a solvent and 1-3 parts of an initiator. The non-fluorine-containing comonomer is a mixture of one of two ingredients selected from a silicon-containing monomer, a long alkyl chain monomer and a hydroxyl monomer. When parts by weight of the modifier and the functional additive are both zero, at least one of the fluorine-containing monomer and the non-fluorine-containing comonomer contains a carbamoyl group. The invention also discloses a preparation method of the polymer containing a carbamoyl group. The polymer containing the carbamoyl group can be used as a waterproof, oil-resistant, antifouling protective agent of stone and has advantages of good durability and weatherability.

Description

A kind of containing carbamyl based polyalcohol and preparation method thereof
Technical field
The present invention relates to polymer arts, particularly relate to a kind of containing carbamyl based polyalcohol and preparation method thereof.
Background technology
Lithotome is a kind of porousness mineral substance, a large amount of microgaps and pore are deposited in its inside, many fluent meterials such as the cement pulp-water when dust in physical environment, acid rain, greasy dirt, colored liquid and wet combining are constructed are as easy as rolling off a log because of pore plane of action infiltration stone material inside, stone product polluted, destroys, cause multiple pathology to produce, as: water spots is not done, the accumulation of salt in the surface soil of saltouing, rust staining tell Huang, frost damage, surface corrosion, colour contamination (comprising greasy dirt), moss growth etc.The appearance of these illnesss makes the load-bearing of the building materials such as stone material or decorate properties disappear, and causes permanent sorry.
Stone protectant is a kind of liquid being used for protecting stone material specially, mainly contains esters of acrylic acid, silicon Class C, silicone based and fluorine silicon class.Wherein esters of acrylic acid and silicon Class C belong to s-generation protective agent; Silicone based is product type main on market, belongs to third generation product.Second, third product Shortcomings in grease proofing and antifouling property in generation.
Use containing fluoro-alkyl (R fbase) compound stone surface is processed, its surface waterproofing, grease proofing and antifouling effect can be given.Such as will with R fthe acrylate of base is coated on cement or stone material and forms protective membrane; With with R fbase phosphoric acid ester process stone material; To comprise containing R fthe polymkeric substance that base monomer and the poly-silica system vinyl monomer accounting for polymer weight fractin 0.1% ~ 1.9% are formed is used as treatment agent etc., but above protective agent still exists waterproof, the problem that grease proofing and antifouling property is not enough.Fluorine silicon class, due to the waterproof of excellence, grease proofing, antifouling and ageing-resistant performance, is Protection Product best at present, is applicable to the surface treatment of all stone materials having particular requirement, is forth generation product.
Chinese patent Authorization Notice No. CN1167756C discloses the fluorine-silicon copolymer thing comprising fluorochemical monomer, silicon-containing monomer, emulsion stability and other monomer, and this multipolymer is used to the water and oil repellant process of stone material.Chinese patent Authorization Notice No. CN 100336837C discloses and will comprise containing fluoro-alkyl (R fbase) monomer and account for the fluorine-silicon copolymer thing of silicon-containing monomer of polymer weight fractin 2.0 ~ 6.0%, this multipolymer is used as masonry-treating agnet.China Patent Publication No. CN102186893A discloses and comprises fluorochemical monomer and as follows:
Containing the fluorine-silicon copolymer thing of sulfydryl silicone.Wherein R 1, R 2, R 3be respectively methyl, methoxyl group, phenyl or hydroxyl; A, B are respectively the divalent straight with 1 ~ 10 carbon atom or straight chain comprises alkyl, do not have ehter bond or be inserted with one or two ehter bond in described saturated hydrocarbyl; C is for having amino, hydroxyl, epoxy group(ing) or carboxyl.This multipolymer is used to the water and oil repellant process of porous matrix.It is the fluorine-silicon copolymer thing comprising fluorochemical monomer and silicon-containing monomer of reaction medium that China Patent Publication No. CN102209735A discloses with silane compound, is used to the water and oil repellant process of porous matrix equally.
The fluorine silicon class stone protectant announced in above patent documentation or current commercially available forth generation fluorine silicon class stone protectant product, the fluorochemical monomer adopted is substantially based on perfluoroalkyl long alkyl chain monomer, although its waterproof, grease proofing and antifouling property is excellent, still needs further improvement in perviousness, weather resistance, weathering resistance.
Summary of the invention
The object of this invention is to provide a kind of containing carbamyl based polyalcohol and preparation method thereof, when this polymkeric substance is used as stone protector, good penetrability, waterproof, grease proofing and antifouling property is excellent and good endurance, and weathering resistance is excellent.
To achieve these goals, present invention employs following technical scheme: a kind of containing carbamyl based polyalcohol, by weight, it consists of:
Described non-fluorine-containing comonomer is one or both the mixture in silicon-containing monomer, long alkyl chain monomer, hydroxyl monomer;
When the parts by weight of described properties-correcting agent and described functional additive are 0, at least one in described fluorochemical monomer and non-fluorine-containing comonomer contains formamyl (-NHCOO-).
Described fluorochemical monomer can represent by formula (3) or formula (4):
Wherein, m4 is 1 or 0, R 3and R 4for H or CH 3.Q 3and Q 4for divalent organic group, as (CH 2) n(n is the integer of 1 ~ 8), CH 2cH 2n (CH 3) SO 2, CH 2cH 2n (CH 2cH 3) SO 2, CH (CH 3) CH 2n (CH 3) SO 2, CH 2cH 2nH, N (CH 3) CH 2cH 2nH etc.R f3and R f4for Polyfluoroalkyl or perfluoropolyether group, Polyfluoroalkyl can be C 1 ~ 20polyfluoroalkyl, preferred C 3 ~ 8polyfluoroalkyl as (CF 2) 2cF 3, CF (CF 3) 2, (CF 2) 3cF 3, CF 2cF (CF 3) 2, C (CF 3) 3, (CF 2) 4h, (CF 2) 2cF (CF 3) 2, (CF 2) 5cF 3, (CF 2) 7cF 3deng; Perfluoropolyether group is as CF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3, CF 2[OCF 2cF 2] poCF 3, C (O) CF (CF 3) (OCF 2cF (CF 3)) po C 3f 7, C (O) CF (OCF 2cF 2) poCF 3deng the PFPE represented, p represents the mean number of repeating unit, and p is 1 ~ 20, is preferably 4 ~ 10.
Fluorochemical monomer shown in formula (3) can by (methyl) vinylformic acid and corresponding polyfluoro alcohol (as HOCH 2cH 2cF 2cF 2cF 2cF 3, HOCH 2cH 2n (CH 3) SO 2cF 2cF 2cF 2cF 3, HOCH 2cF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3, HOCH 2cH 2nHCOCF 2[OCF 2cF 2] poCF 3deng) or polyfluoro amine (as HN (CH 3) CH 2cH 2nHCOCF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3deng) obtain through over-churning or amidate action, also can by (methyl) acrylate (as CH 2=CHCOONa) with corresponding polyfluoro iodide (as ICH 2cH 2cF 2cF 2cF 2cF 3) obtain through the esterification of de-salt compounded of iodine (as NaI).Fluorochemical monomer shown in formula (4) can be obtained through esterification or amidate action by allyl isocyanate or isocyanic ester ethyl propenoate and corresponding polyfluoro alcohol or polyfluoro amine.
Described fluorochemical monomer can be listed below:
CH 2＝CR 1COOCH 2CH 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2CF 2CF(CF 3) 2
CH 2＝CR 1COOCH 2CH 2C(CF 3) 3
CH 2＝CR 1COOCH 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CF 2CF 2CF 2CF 2H
CH 2＝CR 1COOCH 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2N(CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2N(CH 2CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2N(CH 2CH 3)SO 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH(CH 3)CH 2N(CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2N(CH 3)SO 2CF(CF 3) 2
CH 2＝CR 1COOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1COOCH 2CF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1COOCH 2CH 2NHCOCF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOCF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1CON(CH 3)CH 2CH 2NHCOCF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1CON(CH 3)CH 2CH 2NHCOCF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2CF 2CF(CF 3) 2
CH 2＝CR 1CH 2NHCOOCH 2CH 2C(CF 3) 3
CH 2＝CR 1CH 2NHCOOCH 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CF 2CF 2CF 2CF 2H
CH 2＝CR 1CH 2NHCOOCH 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2N(CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2N(CH 2CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2N(CH 2CH 3)SO 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH(CH 3)CH 2N(CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2N(CH 3)SO 2CF(CF 3) 2
CH 2＝CR 1CH 2NHCOOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2NHCOCF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1CH 2NHCOOCH 2CH 2NHCOCF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1CH 2NHCON(CH 3)CH 2CH 2NHCOCF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1CH 2NHCON(CH 3)CH 2CH 2NHCOCF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2CF 2CF(CF 3) 2
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2C(CF 3) 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CF 2CF 2CF 2CF 2H
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2N(CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2N(CH 2CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2N(CH 2CH 3)SO 2CF 2CF 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH(CH 3)CH 2N(CH 3)SO 2CF 2CF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2N(CH 3)SO 2CF(CF 3) 2
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2NHCOCF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3CH 2＝CR 1COOCH 2CH 2NHCOOCH 2CH 2NHCOCF 2[OCF 2CF 2] pOCF 3
CH 2＝CR 1COOCH 2CH 2NHCON(CH 3)CH 2CH 2NHCOCF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3
CH 2＝CR 1COOCH 2CH 2NHCON(CH 3)CH 2CH 2NHCOCF 2[OCF 2CF 2] pOCF 3
Wherein, above various middle R 1for H or CH 3, p represents the mean number of repeating unit, and p is 1 ~ 20, is preferably 4 ~ 10.
Fluorochemical monomer can be the mixture of one or more wherein.Fluorochemical monomer of the present invention is preferably
CH 2＝CHCH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 3、
CH 2＝CHCH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3、
CH 2＝CHCH 2NHCOOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2NHCOOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3、
CH 2＝C(CH 3)COOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2CF 2CF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3、
CH 2＝C(CH 3)COOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3、
In one or both mixture.
Silicon-containing monomer of the present invention can be listed below:
CH 2=CHSi (OC nh 2n+1) 3(vinyl trialkyl oxysilane)
CH 2=CHCH 2si (OC nh 2n+1) 3(anone silane)
CH 2=CR 2cOOCH 2cH 2cH 2si (OC nh 2n+1) 3((methyl) acryloxy propyl trialkoxy silane)
CH 2＝CR 2COOCH 2CH 2OCONHCH 2CH 2CH 2Si(OC nH 2n+1) 3
CH 2＝CR 2CH 2OCONHCH 2CH 2CH 2Si(OC nH 2n+1) 3
Various middle R above 2for H or CH 3, n is the integer of 1 ~ 5.Silicon-containing monomer of the present invention preferably containing the silicon-containing compound of silyl, is more preferably
CH 2＝C(CH 3)COOCH 2CH 2OCONHCH 2CH 2CH 2Si(OCH 2CH 3) 3
CH 2＝CHCH 2OCONHCH 2CH 2CH 2Si(OCH 2CH 3) 3
CH 2=CHCH 2si (OCH 3) 3(vinyltrimethoxy silane)
CH 2=C (CH 3) COOCH 2cH 2cH 2si (OCH 3) 3one in ((methyl) acryloxypropyl Trimethoxy silane).
Long alkyl chain monomer of the present invention can select CH 2=CR 3cOO (CH 2) 11 ~ 17cH 3, CH 2=CHCH 2nHCOO (CH 2) 11 ~ 17cH 3, CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 11 ~ 17cH 3deng.Wherein CH 2=CR 3cOO (CH 2) 11 ~ 17cH 3obtain through esterification by (methyl) vinylformic acid and corresponding fatty alcohol; CH 2=CHCH 2nHCOO (CH 2) 11 ~ 17cH 3can be obtained through esterification by allyl isocyanate and corresponding fatty alcohol; CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 11 ~ 17cH 3can be obtained through esterification by isocyanic ester ethyl propenoate and corresponding fatty alcohol.Described long alkyl chain monomer can be listed below:
CH 2=CR 3cOO (CH 2) 17cH 3((methyl) octadecyl acrylate)
CH 2=CR 3cOO (CH 2) 15cH 3((methyl) Process Conditions of Cetane Acrylate)
CH 2=CR 3cOO (CH 2) 13cH 3((methyl) tetradecyl acrylate)
CH 2=CR 3cOO (CH 2) 11cH 3((methyl) dodecyl acrylate)
CH 2=CHCH 2nHCOO (CH 2) 17cH 3(allyl amino formic acid octadecyl ester)
CH 2=CHCH 2nHCOO (CH 2) 15cH 3(allyl amino formic acid hexadecyl ester)
CH 2=CHCH 2nHCOO (CH 2) 13cH 3(allyl amino formic acid 14 ester)
CH 2=CHCH 2nHCOO (CH 2) 11cH 3(allyl amino first dodecyl gallate)
CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 17cH 3(acryloyl-oxyethyl carboxylamine octadecyl ester)
CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 15cH 3(acryloyl-oxyethyl carboxylamine hexadecyl ester)
CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 13cH 3(acryloyl-oxyethyl carboxylamine 14 ester)
CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 11cH 3(acryloyl-oxyethyl carboxylamine ten diester)
Various middle R above 3for H or CH 3.
Long alkyl chain monomer of the present invention is preferably
CH 2=CHCH 2nHCOO (CH 2) 17cH 3(allyl amino formic acid octadecyl ester)
CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 17cH 3(acryloyl-oxyethyl carboxylamine octadecyl ester)
CH 2=CHCOO (CH 2) 17cH 3(octadecyl acrylate)
CH 2=C (CH 3) COO (CH 2) 17cH 3(stearyl methacrylate)
CH 2=CHCOO (CH 2) 11cH 3(dodecyl acrylate)
In one.
Hydroxyl monomer of the present invention is preferably hydroxyethyl methylacrylate (CH 2=C (CH 3) COOCH 2cH 2or Hydroxyethyl acrylate (CH OH) 2=CHCOOCH 2cH 2oH).
Functional additive of the present invention is preferably 3-mercaptopropyl trimethoxysilane (HSCH 2cH 2cH 2si (OCH 3) 3), one in lauryl mercaptan, mercaptoethanol.
Described properties-correcting agent is preferably isocyanatopropyl triethoxyl silane (OCNCH 2cH 2cH 2si (OC 2h 5) 3) or 2,4 toluene diisocyanate.
Solvent of the present invention is preferably butylacetate or ethyl acetate.
Initiator of the present invention is preferably azo two fourth eyeball.
The present invention also provides this to contain the preparation method of carbamyl based polyalcohol; by fluorochemical monomer 100 ~ 140 parts, non-fluorine-containing comonomer 15 ~ 100 parts, functional additive 0 ~ 5 part, properties-correcting agent 0 ~ 20 part, solvent 400 ~ 600 parts, initiator 1 ~ 3 part; at 60 ~ 85 DEG C, react 3 ~ 15h, obtain containing carbamyl based polyalcohol.
As the preferred embodiment of the present invention, described properties-correcting agent adds after reaction beginning 3 ~ 5h
What the present invention prepared contains carbamyl based polyalcohol, comprises the silyl shown in fluorochemical monomer chain link and formula (1), and the carbamoyl group shown in formula (2):
Wherein, Y 1, Y 2and Y 3can be identical or different, independently represent alkyl, aryl or hydrolysable group; Y 1, Y 2and Y 3in have one at least for hydrolysable group as-Si (OCH 3) 3,-Si (OCH 2cH 3) 3,-Si (CH 3) (OCH 3) 2,-Si (CH 3) 2(OCH 3) ,-Si (ON (CH 3) C 2h 5) 3,-Si (CH 3) (ON (CH 3) C 2h 5) 2,-Si (CH 3) 2(ON (CH 3) C 2h 5) ,-Si (OCOCH 3) 3,-Si (CH 3) (OCOCH 3) 2,-Si (CH 3) 2(OCOCH 3) etc., preferred Y 1, Y 2and Y 3be hydrolysable group; M2 be 1 or 0, n2 be positive integer, R 2for H or CH 3.
Fluorochemical monomer chain link is that polymkeric substance provides waterproof, grease proofing and antifouling property, is the main ingredient of polymkeric substance; Silyl shown in formula (1) contains hydrolysable group, can produce chemical bonding with base material, improves the cohesive force of polymeric coating and base material.With the polymer phase ratio not containing carbamoyl group, the polymer permeability containing the carbamoyl group shown in formula (2) improves, and makes the waterproof of coating, grease proofing and antifouling weather resistance more excellent.
Silyl containing carbamyl based polyalcohol can carry out the monomer segments of self-contained silyl; also the functional additive of self-contained silyl can be carried out; the properties-correcting agent of self-contained silyl can also be carried out, usually require that monomer, functional additive and properties-correcting agent at least one contain silyl.Containing monomer and the silicon-containing monomer of silyl.Containing the functional additive of silyl as 3-mercapto propyl trialkoxy silane (HSCH 2cH 2cH 2si (OC nh 2n+1) 3) etc., n is the integer of 1 ~ 4.Containing the properties-correcting agent of silyl as isocyanatopropyl trialkoxy silane (OCNCH 2cH 2cH 2si (OC nh 2n+1) 3) etc., n is the integer of 1 ~ 4.
Carbamoyl group containing carbamyl based polyalcohol can from the side chain of polymer macromolecule chain or/and in end chain structure.Formamyl in side-chain structure can by the monomer copolymerization introducing polymer macromolecule structure containing formamyl, and the suitable polymer also can passing through to contain pendant hydroxyl group or amino is reacted with the properties-correcting agent containing isocyanate groups and introduced.Formamyl in end chain structure can be introduced by the functional additive containing formamyl, also reacts by the suitable polymer containing terminal hydroxy group or amino and the properties-correcting agent containing isocyanate groups and introduces.Properties-correcting agent containing isocyanate groups is selected from OCNCH 2cH 2cH 2si (OC nh 2n+1) 3, vulcabond, polyisocyanates etc., n is the integer of 1 ~ 4.Vulcabond as tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,5-naphthalene diisocyanate (NDI), tetramethyl-vulcabond (TMXDI), hexamethylene diisocyanate (HDI), to phenyl diisocyanate (PPDI), dimethylenebenzene vulcabond (XDI) etc.; Polyisocyanates is as TDI, MDI tripolymer etc.
Obtain by free radical solution copolymerization containing carbamyl based polyalcohol, the polymkeric substance also prepared by free radical solution copolymerization obtains through radical reaction modification again.When being obtained by free radical solution copolymerization, in comonomer or functional additive, at least one reactant contains carbamoyl group.When being obtained by modification, usually require containing hydroxyl or amino isoreactivity group in polymer macromolecule, containing isocyanate groups in properties-correcting agent.
The formamyl polymer dissolution that contains of the present invention forms stone protectant in suitable solvent, and first will be diluted to certain concentration during use, this concentration is determined according to concrete stone material product and operation, is generally 0.1% ~ 2.5%; Add appropriate catalyzer again, be generally 0.5 ‰ ~ 5 ‰ containing formamyl polymer loading, and mix; Then adopt suitable method stone protectant to be coated on the surface of stone material, the method can passing through to spray, impregnating is suitable realizes; Finally at the temperature of 20 ~ 200 DEG C, remove desolventizing, and make polymer cure obtain the protective coating of stone material.Described catalyzer plays the effect accelerating solidification in the solidification process of polymkeric substance, can select organic tin compound, organic titanium compounds, acetylacetone metallic compound etc., as: dibutyl tin dilaurate ((C 11h 23cOO) 2sn (C 4h 9) 2), dibutyltin diacetate ((CH 3cOO) 2sn (C 4h 9) 2), dibutyl two (dodecyl sulphur) tin ((C 12h 25s) 2sn (C 4h 9) 2), dibutyl toxilic acid tin ((OOC CH 2cH 2cOO) Sn (C 4h 9) 2), stannous octoate ((C 7h 15cOO) 2sn), tetra-n-butyl titanate (Ti (O (CH 2) 3cH 3) 4), titanium isopropylate (Ti (OCH (CH 3) 2) 4), metatitanic acid four tert-butyl ester (Ti (OC (CH 3) 3) 4), two (acetylacetone based) metatitanic acid diisopropyl ester ((CH 3cOCH=C (CH 3) O) 2ti (OCH (CH 3) 2) 2), two (acetylacetone based) isobutoxy isopropoxy titanic acid ester ((CH 3cOCH=C (CH 3) O) 2ti (OCH (CH 3) 2) (OCH 2cH (CH 3) 2)), two (acetylacetone based) oxyethyl group isopropoxy titanic acid ester ((CH 3cOCH=C (CH 3) O) 2ti (OCH 2cH 3) (OCH (CH 3) 2)), aluminium acetylacetonate (Al (CH 3cOCH=C (CH 3) O) 3) etc., wherein more preferably dibutyl tin dilaurate, dibutyltin diacetate, titanium isopropylate, two (acetylacetone based) metatitanic acid diisopropyl ester, aluminium acetylacetonate etc.
The present invention, owing to have employed technique scheme, when being used as stone protector, has following beneficial effect:
1, of the present invention containing carbamyl based polyalcohol, good penetrability, waterproof, grease proofing and antifouling excellent durability, and good weatherability, fluorochemical monomer chain link is that polymkeric substance provides waterproof, grease proofing and antifouling property; Silyl contains hydrolysable group, can produce chemical bonding with base material, improves the cohesive force of polymeric coating and base material; With the polymer phase ratio not containing carbamoyl group, polymer permeability containing carbamoyl group improves, and make the waterproof of coating, grease proofing and antifouling weather resistance more excellent, coating is greater than 113 ° to water initial contact angle, is greater than 62 ° to white mineral oil contact angle, and before and after weather resistance and weathering resistance experiment, contact angle change is less than 10%, resistance to soiling change of rank is no more than 2 grades; Initial fouling resistance rating is more than 4, and after weather resistance and weathering resistance experiment, fouling resistance rating is still more than 3;
2, preparation method's technique is simple, and transformation efficiency is high.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
The present invention is raw materials used all can be commercially available or prepare, and wherein part material preparation method is as follows:
Synthesis example 1 (CH 2=CHCH 2nHCOOCH 2cH 2cF 2cF 2cF 2cF 3synthesis---F1)
The HOCH of 264g (1mol) is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 2cH 2cF 2cF 2cF 2cF 3(purchased from Heng Tong fluorine chemistry, TEOH-4), drips the CH of 83g (1mol) under normal temperature and agitation condition 2=CHCH 2nCO (purchased from land for growing field crops, Beijing Feng Tuo chemical technology company limited), 30min dropwises, add a small amount of Resorcinol (purchased from Nanjing Xin Huayuan Chemical Co., Ltd.) stopper again, post-heating is warming up to 80 DEG C of reaction 8h, obtains light yellow clear liquid.Infrared analysis shows the completely dissolve of isocyanate groups absorption peak.
Synthesis example 2 (CH 2=CHCH 2nHCOOCH 2cH 2cF 2cF 2cF 2cF 2cF 2cF 3synthesis---F2)
Except the HOCH with 364g (1mol) 2cH 2cF 2cF 2cF 2cF 2cF 2cF 3(purchased from Heng Tong fluorine chemistry, TEOH-6) substitutes the HOCH of 264g (1mol) 2cH 2cF 2cF 2cF 2cF 3outward, other is with synthesis example 1.
Synthesis example 3 (CH 2=CHCOOCH 2cH 2nHCOOCH 2cH 2cF 2cF 2cF 2cF 3synthesis---F3)
Except the CH with 141g (1mol) 2=CHCOOCH 2cH 2nCO (purchased from Zouping Mingxing Chemical Co., Ltd.) substitutes the CH of 83g (1mol) 2=CHCH 2outside NCO, other is with synthesis example 1.
Synthesis example 4 (CH 2=CHCOOCH 2cH 2nHCOOCH 2cH 2cF 2cF 2cF 2cF 2cF 2cF 3synthesis---F4)
The HOCH of 364g (1mol) is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 2cH 2cF 2cF 2cF 2cF 2cF 2cF 3, under normal temperature and agitation condition, drip the CH of 141g (1mol) 2=CHCOOCH 2cH 2nCO, 30min dropwise, then add a small amount of Resorcinol stopper, and post-heating is warming up to 80 DEG C of reaction 8h, obtains light yellow clear liquid.Infrared analysis shows the completely dissolve of isocyanate groups absorption peak.
Synthesis example 5 (CH 2=CHCH 2nHCOOCH 2cF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3synthesis, p represents the mean number of repeating unit, and P is 4---F5)
The HOCH of 902g (1mol) is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 2cF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3(p represents the mean number of repeating unit, and p is 4) (purchased from Juhua Group Co.), drips the CH of 83g (1mol) under normal temperature and agitation condition 2=CHCH 2nCO, 30min dropwise, then add a small amount of Resorcinol stopper, and post-heating is warming up to 80 DEG C of reaction 8h, obtains light yellow clear liquid.Infrared analysis shows the completely dissolve of isocyanate groups absorption peak.
Synthesis example 6 (CH 2=CHCOOCH 2cH 2nHCOOCH 2cF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3synthesis, p represents the mean number of repeating unit, and p is 5.3---F6)
The HOCH of 1196g (1mol) is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 2cF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3(p represents the mean number of repeating unit, and p is 5.3), under normal temperature and agitation condition, drip the CH of 141g (1mol) 2=CHCOOCH 2cH 2nCO, 30min dropwise, then add a small amount of Resorcinol stopper, and post-heating is warming up to 80 DEG C of reaction 8h, obtains light yellow clear liquid.Infrared analysis shows the completely dissolve of isocyanate groups absorption peak.
Synthesis example 7 (CH 2=C (CH 3) COOCH 2cF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3synthesis, p represents the mean number of repeating unit, and p is 10---F7)
The HOCH of 2257g (1mol) is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 2cF (CF 3) [OCF 2cF (CF 3)] poCF 2cF 2cF 3the CH of (P represents the mean number of repeating unit, and p is 10), 95g (1.1mol) 2=C (CH 3) COOH (purchased from Suzhou Guan Hui Chemical Co., Ltd.), appropriate water entrainer and a small amount of Resorcinol stopper and a small amount of Catalyzed by p-Toluenesulfonic Acid agent, under agitation be warming up to 120 DEG C and carry out esterification, to the water in water separator close to theoretical value time, esterification is complete.Then go out water entrainer and unreacted methacrylic acid respectively by air distillation and underpressure distillation, then go out catalyzer and stopper by washing, vacuum-drying obtains target product.
Synthesis example 8 (CH 2=C (CH 3) COOCH 2cH 2oCONHCH 2cH 2cH 2si (OCH 2cH 3) 3synthesis---S1)
The OCNCH of 247g (1mol) is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 2cH 2cH 2si (OCH 2cH 3) 3(purchased from Nanjing Neng De Chemical Co., Ltd.), drips the CH of 130g (1mol) under normal temperature and agitation condition 2=C (CH 3) COOCH 2cH 2oH (purchased from the prosperous oil paint additive factory in Dongming County), 30min dropwises, then adds a small amount of Resorcinol stopper, and post-heating is warming up to 80 DEG C of reaction 8h, obtains colourless transparent liquid.Infrared analysis shows the completely dissolve of isocyanate groups absorption peak.
Synthesis example 9 (CH 2=CHCH 2oCONHCH 2cH 2cH 2si (OCH 2cH 3) 3synthesis---S2)
Except the CH with 58g (1mol) 2=CHCH 2oH (purchased from Hangzhou Fang Sheng Chemical Co., Ltd.) substitutes the CH of 130g (1mol) 2=C (CH 3) COOCH 2cH 2outside OH, all the other are with synthesis example 8.
Synthesis example 10 (CH 2=CHCH 2nHCOO (CH 2) 17cH 3synthesis---M1)
HO (the CH of 270g (1mol) is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 2) 17cH 3(purchased from Zhengzhou Bang Nuo Chemicals company limited), drips the CH of 83g (1mol) under normal temperature and agitation condition 2=CHCH 2nCO, 30min dropwise, then add a small amount of Resorcinol stopper, and post-heating is warming up to 80 DEG C of reaction 8h, obtains white waxy solid.Infrared analysis shows the completely dissolve of isocyanate groups absorption peak.
Synthesis example 11 (CH 2=CHCOOCH 2cH 2nHCOO (CH 2) 17cH 3synthesis---M2)
Except the CH with 141g (1mol) 2=CHCOOCH 2cH 2nCO substitutes the CH of 83g (1mol) 2=CHCH 2outside NCO, other is with synthesis example 10.
The compound of other abbreviation coded representation is as follows:
F8:CH 2=CHCOOCH 2cH 2cF 2cF 2cF 2cF 3(purchased from Heng Tong fluorine chemistry, TEAc-4)
F9:CH 2=CHCOOCH 2cH 2cF 2cF 2cF 2cF 2cF 2cF 2cF 2cF 3(purchased from Juhua Group Co.)
F10:CH 2=C (CH 3) COOCH 2cH 2cF 2cF 2cF 2cF 2cF 2cF 3(purchased from Juhua Group Co.)
S3:CH 2=CHCH 2si (OCH 3) 3(purchased from Shanghai to prosperous Chemical Co., Ltd.)
S4:CH 2=C (CH 3) COOCH 2cH 2cH 2si (OCH 3) 3(purchased from Nanjing Neng De Chemical Co., Ltd., KH-570)
M3:CH 2=CHCOO (CH 2) 17cH 3(purchased from Zhejiang Kant's novel material company limited)
M4:CH 2=C (CH 3) COO (CH 2) 17cH 3(purchased from Zhejiang Kant's novel material company limited)
M5:CH 2=CHCOO (CH 2) 11cH 3(purchased from Zhejiang Kant's novel material company limited)
HEMA:CH 2=C (CH 3) COOCH 2cH 2oH (purchased from the prosperous oil paint additive factory in Dongming County)
HEA:CH 2=CHCOOCH 2cH 2oH (purchased from the prosperous oil paint additive factory in Dongming County)
KH-580:HSCH 2cH 2cH 2si (OCH 3) 3(purchased from Nanjing Neng De Chemical Co., Ltd., KH-580)
KH-125:OCNCH 2cH 2cH 2si (OC 2h 5) 3(purchased from Nanjing Neng De Chemical Co., Ltd., KH-125)
HS: lauryl mercaptan (purchased from Shanghai Jin Yue Chemical Co., Ltd.)
MCH: mercaptoethanol (purchased from Nanjing Pu Ding Chemical Co., Ltd.)
AIBN: azo two is fourth eyeball (purchased from Shanghai Hao Hua Chemical Co., Ltd.)
TDI: Toluene-2,4-diisocyanate, 4-vulcabond (purchased from Yantai ten thousand China)
Embodiment 1
40g F1,100g F9,25g S3,500g ethyl acetate and 3g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 80 DEG C of reaction 4h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 2
20g F3,110g F8,15g S4,500g butylacetate and 2.5g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 70 DEG C of reaction 6h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 3
30g F1,100g F2,20g S3,50g M3,550g butylacetate and 3g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 70 DEG C of reaction 6h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 4
100g F10,25g S2,75g M4,550g butylacetate and 2.8g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 60 DEG C of reaction 10h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 5
100g F5,30g S4,70g M5,550g butylacetate and 2.8g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 85 DEG C of reaction 3h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 6
125g F6,25g S1,50g M4,550g ethyl acetate and 2.5g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 7
100g F4,30g F7,10g S3,60g M2,550g butylacetate and 2g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 8
75g F4,65g F9,20g S2,40g M1,550g ethyl acetate and 1.5g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 9
120g F10,25g S1,500g butylacetate and 1g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 10
130g F8,30g S2,500g butylacetate and 2g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 11
100g F5,30g S4,70g M5,550g butylacetate and 1.8g AIBN, 1g HS is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 12
100g F9,20g S1,80g M3,520g butylacetate and 1.5g AIBN, 1g HS is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 13
120g F9,60g M3,6.4g HEA, 600g butylacetate and 1.5g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h.Then be cooled to 35 DEG C, in 10min, drip 13.6g KH-125, then be warming up to 85 DEG C of reaction 10h, namely obtain of the present invention containing carbamyl based polyalcohol.
Embodiment 14
115g F10,55g M4,11g HEMA, 520g butylacetate and 1.8g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h.Then be cooled to 35 DEG C, in 10min, drip 20g KH-125, then be warming up to 85 DEG C of reaction 10h, namely obtain of the present invention containing carbamyl based polyalcohol.
Embodiment 15
130g F10,50g M4,6.9g HEMA, 520g butylacetate and 1.8g AIBN is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h.Then be cooled to 35 DEG C, in 10min, drip 13.1g KH-125, then be warming up to 85 DEG C of reaction 10h, namely obtain of the present invention containing carbamyl based polyalcohol.
Embodiment 16
120g F10,60g M4,6.9g HEMA, 520g butylacetate and 1.3g AIBN, 1g MCH is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h.Then be cooled to 35 DEG C, in 10min, drip 13.1g KH-125, then be warming up to 85 DEG C of reaction 10h, namely obtain of the present invention containing carbamyl based polyalcohol.
Embodiment 17
70g F8,55g F9,70g M2,400g butylacetate and 1g AIBN, 5g KH-580 is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 18
70g F8,55g F9,10g S2,63g M3,520g butylacetate and 1.5g AIBN, 2g KH-580 is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains of the present invention containing carbamyl based polyalcohol.
Embodiment 19
50g F8,80g F9,60g M3,520g butylacetate and 1.3g AIBN, 2.4g MCH is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h.Then be cooled to 35 DEG C, in 10min, drip 7.6g KH-125, then be warming up to 85 DEG C of reaction 10h, namely obtain of the present invention containing carbamyl based polyalcohol.
Embodiment 20
120g F10,58g M4,8.6g HEMA, 520g butylacetate and 1.3g AIBN, 2g KH-580 is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h.Then be cooled to 35 DEG C, in 10min, drip 11.4g TDI, then be warming up to 85 DEG C of reaction 10h, namely obtain of the present invention containing carbamyl based polyalcohol.
Comparative example 1
125g F is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 9, 25g S3,50g M3,550g ethyl acetate and 2.5g AIBN.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains not containing carbamyl based polyalcohol.
Comparative example 2
125g F is added in the 1L tetra-mouthfuls of reaction flasks being equipped with agitator, constant temperature oil bath, thermometer and condenser 10, 25g S4,50g M4,550g ethyl acetate and 2.5g AIBN.Reactor nitrogen replacement 3 times, is then warming up to 75 DEG C of reaction 5h, namely obtains not containing carbamyl based polyalcohol.
Base material treatment method
It is 1% that the polymers soln solvent sherwood oil that above-described embodiment 1 ~ 20 and comparative example 1 ~ 2 obtain is diluted to mass concentration, add the catalyzer accounting for polymer quality number 2 ‰ again, wherein embodiment 1 ~ 4, 13, 14, 19, 20 catalyzer added are acid dibutyl tin, the catalyzer that embodiment 5 ~ 7 adds is dibutyltin diacetate, embodiment 8, 15 catalyzer added are titanium isopropylate, the catalyzer that embodiment 9 ~ 12 adds is two (acetylacetone based) metatitanic acid diisopropyl ester, the catalyzer that embodiment 16 ~ 18 adds is aluminium acetylacetonate, the surface of various stone material is coated on after mixing, at room temperature except desolventizing, and continuation placement 24h makes polymer cure obtain the protective coating of stone material.
Performance test methods
(1) contact angle test
To process and base material contact angle instrument that non-processor is crossed carries out the contact angle test of deionized water (W) and white mineral oil (O).Replicate(determination) 5 times, averages.
(2) resistant test
Pollutent is placed on and processed and on untreated base material, after placing 24h, wiped drop with paper handkerchief.Resistance to soiling evaluation is carried out according to the depth of stain and the size of range of scatter:
1=stain is dark, oil droplet diffusion scope is larger
2=stain is dark, oil droplet diffusion scope is little or without diffusion
3=moderate stain, oil droplet diffusion scope are little
The slight stain of 4=, oil droplet are without diffusion
5=free from smutting during, oil droplet are without diffusion
(3) durability test
The base material abrasion test instrument processed (load is 250g) is carried out the wearing test of 300 turns, the base material after wearing and tearing carries out the test of contact angle and resistance to soiling again.Be less than 10% with contact angle change before and after wearing test, resistance to soiling change of rank is no more than 2 for qualified.
(4) weathering resistance test
The weather resistance test processing base material performs with reference to GB/T 1865-2009 " paint and varnish artificial weathering and man-made radiation expose the xenon arc radiation of filtration to the open air ", use the xenon lamp [method 1 (artificial weathering)] of daylight filter, model Wetting cycle adopts A pattern, and continuous exposure duration is 2000h.After atmospheric exposure test, again contact angle test is carried out to the base material processed, be less than 10% with contact angle change before and after weathering test, resistance to soiling change of rank is no more than 2 for qualified.
The contact angle test of table 1 marble base material
The resistance to soiling test of table 2 marble base material

Claims (9)

1., containing a carbamyl based polyalcohol, it is characterized in that by weight, it consists of:
Described non-fluorine-containing comonomer is one or both the mixture in silicon-containing monomer, long alkyl chain monomer, hydroxyl monomer;
When the parts by weight of described properties-correcting agent and functional additive are 0, at least one in described fluorochemical monomer and non-fluorine-containing comonomer contains formamyl.
2. according to claim 1 containing carbamyl based polyalcohol, it is characterized in that described fluorochemical monomer is
CH 2＝CHCH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 3、
CH 2＝CHCH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2NHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3、
CH 2＝CHCH 2NHCOOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2NHCOOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3、
CH 2＝C(CH 3)COOCH 2CF(CF 3)[OCF 2CF(CF 3)] pOCF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2CF 2CF 2CF 2CF 3、
CH 2＝CHCOOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3、
CH 2＝C(CH 3)COOCH 2CH 2CF 2CF 2CF 2CF 2CF 2CF 3、
In one or both mixture, wherein p represents that the mean number of repeating unit is 4 ~ 10.
3. according to claim 1 containing carbamyl based polyalcohol, it is characterized in that described silicon-containing monomer is
CH 2＝C(CH 3)COOCH 2CH 2OCONHCH 2CH 2CH 2Si(OCH 2CH 3) 3、
CH 2＝CHCH 2OCONHCH 2CH 2CH 2Si(OCH 2CH 3) 3、
CH 2＝CHCH 2Si(OCH 3) 3、
CH 2＝C(CH 3)COOCH 2CH 2CH 2Si(OCH 3) 3
In one.
4. according to claim 1 containing carbamyl based polyalcohol, it is characterized in that described long alkyl chain monomer is
CH 2＝CHCH 2NHCOO(CH 2) 17CH 3、
CH 2＝CHCOOCH 2CH 2NHCOO(CH 2) 17CH 3、
CH 2＝CHCOO(CH 2) 17CH 3、
CH 2＝C(CH 3)COO(CH 2) 17CH 3、
CH 2＝CHCOO(CH 2) 11CH 3
In one.
5. according to claim 1 containing carbamyl based polyalcohol, it is characterized in that described hydroxyl monomer is hydroxyethyl methylacrylate or Hydroxyethyl acrylate.
6. according to claim 1 containing carbamyl based polyalcohol, it is characterized in that described functional additive is the one in 3-mercaptopropyl trimethoxysilane, lauryl mercaptan, mercaptoethanol; Described properties-correcting agent is isocyanatopropyl triethoxyl silane or 2,4 toluene diisocyanate.
7. according to claim 1 containing carbamyl based polyalcohol, it is characterized in that described solvent is butylacetate or ethyl acetate; Described initiator is azo two fourth eyeball.
8. the preparation method containing carbamyl based polyalcohol according to claim 1; it is characterized in that fluorochemical monomer 100 ~ 140 parts, non-fluorine-containing comonomer 15 ~ 100 parts, functional additive 0 ~ 5 part, properties-correcting agent 0 ~ 20 part, solvent 400 ~ 600 parts, initiator 1 ~ 3 part; at 60 ~ 85 DEG C, react 3 ~ 15h, obtain containing carbamyl based polyalcohol.
9. the preparation method containing carbamyl based polyalcohol according to claim 8, is characterized in that described properties-correcting agent adds after reaction beginning 3 ~ 5h.
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