HK1004752B

HK1004752B - Primer

Info

Publication number: HK1004752B
Application number: HK98103941.7A
Authority: HK
Inventors: Parrinello Giovanni; Simon Hubert; Mulhaupt Rolf
Original assignee: 范蒂科股份公司
Priority date: 1989-06-13
Filing date: 1998-05-07
Publication date: 1998-12-04

Description

The present invention relates to nitrogen silanes used as adhesives and to one or two-component polyurethane resins containing these adhesives and used as adhesives, sealants, coatings or insulators.

Err1:Expecting ',' delimiter: line 1 column 199 (char 198)

Furthermore, cyclic aminals are described in US Patents 3,787,416 and 4,289,869 as hardeners for polyurethane resins. From US Patent 4,404,379 are known conversion products of cyclic aminals with isocyanates into adducts suitable as hardeners for polyurethane resins. However, these aminals or aminal ducts do not contain silane-containing groups.

A class of compounds has now been found which are added to 1- or 2-component polyurethane resins adhesives, sealants, coatings and insulators, achieving a significantly increased adhesion to glass, metal, lacquered steel and plastics, while not affecting or even increasing the curing rate.

The present invention relates to compounds of general formula I Other In which R1C2-C3 Alkyl R2Hydrogen, unsubstituted or substituted by -OH, -CN or -Si ((OR3) 3-qR4q C1-C6-alkyl or C2-C6-alkenyl,R3C1-C4-alkyl or two residues R3 together C1-C4-alkyl,R4C1-C4-alkyl or phenyl andq, the values being 0 to 2, and any remainder of the formula with R5 in the sense of hydrogen or C1-C4-alkyl and R6 in the sense of hydrogen or R5 and R6 together in the sense of C4-C8-alkyl or together with R2 a residue of the formula means in which R7Hydrogen, C1-C4-alkyl or -R9-Si ((OR3) 3-qR4q with R3, R4 and q in the above meanings andR9C1-C8-alkyl means andR8a residue The Commission has R10Hydrogen or C1-C4 alkyl and R11Hydrogen or R10 and R11 together constitute C4-C8 alkyl, and A (CH2) r-O with r equal to 1, 2 or 3 and p equal to 0 or 1 andY means oxygen or sulphur; and In which Teinen residue -R9-Si ((OR3) 3-qR4q, a residue of the formula or, if R7 is a residue of the formula -R9-Si(OR3)3-qR4q and m has a value of 2, an m-value residue Z, wherein R3, R4, R9, Y and q have the above meanings, is X-S or -NH- and is an organic residue derived from a polyisocyanate or polyisothiocyanate with at least 2 NCO or NCS groups, and furthermore means a value of 1 and no value of 1.

Preferably R10 means C1-C4 alkyl.

For example, if R3, R4, R5, R7 and R10 are C1-C4 alkyl or R2 is C1-C6 alkyl, these are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl and for R2 additionally n-pentyl or n-hexyl.

The preferred meaning of R3 and R4 as alkyl is methyl and ethyl, especially methyl.

For example, these include methylene, ethylene, propylene, trimethylene, tetramethylene, 2-methyl-1,3-trimethylene for R3 and R9 and for R9 in addition, and for R5/R6 and R10/R11 together with R11 C4-C8 alkyl and R9 C1-C8 alkyl, these are straight-chain or branched alkyl, with the straight-chain alkyl being preferred.

Preferably, R3 means ethylene, R5/R6 and R10/R11 means tetramethylenes and pentamethylenes and R9 means C1-C4 alkyl groups, especially trimethylenes or ethylene.

If R2 means C2-C6-alkenyl, it is a straight chain or branched alkenyl, preferably a straight chain alkenyl containing one or more but preferably a double bond, such as vinyl, allyl, n-butenyl, 1,3-butadienyl, i-pentenyl, n-pentenyl or n-hexenyl.

If R2 is substituted as a C1-C6-alkyl by OH, CN or Si ((OR3) 3-qR4q groups, it may be a single or multiple substitution, with a single substitution being preferred.

If E is a remainder of the formula Other R2 is preferably C1-C4 alkyl, especially methyl.

The parameter p in formula I is preferably 0.

Also preferably, the parameter q has a value of 0.

The remainder Z is derived from a polyisocyanate or polyisothiocyanate with at least 2 NCO or NCS groups. This NCO or NCS functionality 2 of the polyisocyanate or polyisothiocyanate is obtained by converting, for example, polyamines such as aminoterminated polyether polyoles by phosgeneation or thiophosgeneation to polyisocyanates or polyisocyanates with a functionality 2. The polyisocyanate or polyisocyanate thus obtained can be used either directly or first with diols, polyols, dimercaptanes, diamines or polyamines termed NCO or NCS or prisocyanates in a similar manner.

Another way to produce polyisocyanates with NCO functionality 2 is to oligomerize diisocyanates, for example, diisocyanates such as hexamethylenediisocyanate can be converted by partial hydrolysis to products containing biuret groups (such as Bayer's Desmodur® N100).

Furthermore, diisocyanates such as hexamethylenediisocyanate can be partially trimered to produce higher functional polyisocyanates containing isocyanate rings such as Bayer's Desmodur® N3200.

Chain extension by translating diisocyanates with polyfunctional H-acid compounds with functionality 2 such as triols, tetroles, pentols, triamines, polyamines or polymer captans also results in polyisocyanates with NCO functionality 2.

The diisocyanates are aromatic as well as aliphatic, heterocyclic, monocyclic and polycyclic bifunctional isocyanate compounds, such as toluyl isocyanate, diphenyl methandiisocyanate, naphthyl isocyanate, xylenediisocyanate, hexamethylenediisocyanate, trimethyl hexamethylenediisocyanate, isophorisocyanate or dicylohexylmethandiisocyanate.

The parameters m and n have the values 1 to 49, preferably 1 to 9, particularly 1 to 5, and particularly 1, 2 and 3.

The residue Z preferably has a mean molecular weight Mn < 10000 and in particular Mn < 4000.

Y is preferably equal to 0.

The preferred compounds correspond to formula I, wherein Z is derived from an aliphatic, cycloaliphatic, aliphatic/aromatic, aromatic or heterocyclic polyisocyanate or polyisothiocyanate with 2 NCO or NCS groups, wherein this residue Z may contain one or more ester, ether, urethane, thiourethane, isocyanate, urea or biuret functions, as appropriate.

In particular, preferred compounds correspond to formula I, where Z is derived from an aliphatic or mixed aliphatic/aromatic polyisocyanate with 2 NCO groups, wherein this residue Z contains one or two ester, ether, urethane, thiourethane, isocyanate, urea or biuret functions, as appropriate.

If Z contains etheric oxygen in the compounds of formula I, it may be monoether or oligoether, such as a group of formula Other or (CH2CH2CH2CH2-O) y, where y is a number from 1 to 80, preferably 1 to 20.

Where the residue Z is contained in compounds of the formula I carbamates or thiocarbamates, these are derivatives obtained by conversion of polyols containing compounds containing isocyanate or isothiocyanate groups. Other or Other The following table shows the total number of polyols in the product.

For example, OH-terminated polyethers or polyester can also be used as polyoles.

In preferred compounds of formula I, the residue Z contains two, in particularly preferred compounds an ester, carbamate, isocyanate, urea or biuret functions. The ether functions are a certain exception, as they are capable of forming oligoether bridges, as shown above.

Compounds of formula I are preferred, where E together with R2 constitute a residue of the formula Other R1 is ethylene.

Also preferred are compounds of formula I, where E is a residue of formula Other means, in particular, those in which R5 means isopropyl or tert. Butyl or R5 together with R6 means tetramethyl or pentamethyl.

Another preferred embodiment is compounds of formula I, where T is a residue of the formulae -R9-Si ((OR3) 3-qR4q or Other means, in particular, those in which at least one residue is X-S.

Special preference is given to compounds of formula I, where p is 0 and m is 1, E is a residual. Other with R5 as C3 or C4 alkyl and R2 as C1 to C4 alkyl.

The preparation of the compounds of formula I is done in a self-evident way and can be most easily represented by the following reaction schemes.

I. Aminal or imine-aminated part

This method is for example performed in the manner described in US Patent 4,404,379. The educts (A) and (B) are known compounds, some of which are commercially available or can be produced in a simple, known way. As educts (A) are particularly suitable 3-methylaminopropylamine and 3-(2-aminoethylamino) propyltrimethoxylane. As educts (B), for example, the carbonyl compounds formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pivalaldehyde, cyclopentane or cyclohexanone can be considered.

The conversion of (c) to compounds with reactive double bonds, such as acrylonitrile, in the manner described in EP-A 70536, can produce amines of formula (E), where the residues R2 may have different meanings independently. Other

The resulting aminals (C) and (E) and imine-amines (D) can be converted into a further step with a polyisocyanate Z ((NCO) 2 or a polyisothiocyanate Z ((NCS) 2.

The Commission shall adopt the implementing acts referred to in Article 11 (2).

Err1:Expecting ',' delimiter: line 1 column 288 (char 287)

The following shall be added to the list of active substances:

The manufacture of these components is based on known literature methods, such as those described in USPS 3,492,330; GB-PS 994,890; DE-PS 1,022,789; DE-PS 1,222,067; DE-PS 1,027,394; DE-OS 1,929,034; DE-OS 2,004,048; USPS 3,394,164; DE-PS 1,101,394; GB-PS 889,050; BE-PS 723,640; GB-PS 956,474; GB-PS 1,072,956; USPS 3,567,763 or DE-PS 1,231,688.

Err1:Expecting ',' delimiter: line 1 column 288 (char 287)

IV. Transformation of the polyisocyanate or polyisothiocyanate according to III. with the aminals (C) and/or (E) and the imine amines (D) respectively and with the silanes according to II. to the compounds of formula I.

The conversion of the polyisocyanate or polyisothiocyanate to the other two components may be done successively or in combination. In a stepwise conversion, the amine or imine-amine compound may be first converted to the polyisocyanate or polyisothiocyanate and then the adduct to the alkoxysilan or vice versa. It is also possible to add different amine, imine-amine, silane components to the polyisocyanate or -thiocyanate, whereby the different components may be converted silently, i.e. firstly by adding one silane, then by adding the amine or imine-amine and finally by adding the second silane.

The implementation is usually done without solvent, but if necessary, one or all components can be diluted with an appropriate inert solvent, e.g. to adjust the viscosity to the requirements.

The addition itself is carried out at temperatures between 15°C and 200°C, but preferably at temperatures between 30°C and 140°C.

The reaction can be traced by infrared spectroscopy or titration.

In addition reactions, catalysts of the known type may be used, such as tertiary amines such as triethylamine, N-methyl morpholine, N,N,N',N'-tetramethyl-ethylenediamine or 1,4-diaza-bicyclo- ((2,2,2) -octane.

Examples of organic tin compounds are tin ((II) salts of carbonic acids, such as tin ((II) acetate, tin ((II) octoate and tin ((II) laurate, or the dialkyl tin salts of carbonic acids, such as dibutyl tin indium acetate, dibutyl tin diurate or dioctyl tin indium acetate.

The stoichiometric ratios for the addition of the aminal and aminal and silane components to the polyisocyanate and thiocyanate respectively are maintained such that the ratio of the NH and NH2 groups of the aminal and aminal amines and the NH2 and SH groups of the silanes is approximately equimolar to the NCO and NCS groups of the polyisocyanate and thiocyanate respectively.

The first step is usually performed with a ratio of NH or NH2 or SH groups to NCO or NCS groups of less than 1. The preferred ratio of Amminal or Iminal NH2/NCO or NCS is between 1:2 to 1:6, in particular 1:3 and 1:5 respectively. The preferred ratio of SCO-NH2-SH2 or NCS is between 1:2 and 1:5, in particular 2:3 and 1:3 respectively.

In the second step, the remaining free NCO or NCS groups are usually de-reacted with the aminal-NH or iminamine-NH2 or silane-NH2 or SH groups, and the stoichiometric ratio of the H-acid groups to the NCO or NCS groups is 1, preferably 4:1 to 1:1, and in particular 2:1 to 1:1.

However, it is also possible that the remaining free NCO or NCS groups will only partially react in the second step, and the same stoichiometric conditions as in the first step of addition will apply, preferably when two or more different aminal, iminin-aminal or silan compounds are added.

The compounds of the invention can be used as adhesive agents in polyurethane resins. Their use in moisture-hardening polyurethane resins, which are used as adhesives, sealants, lacquers or insulators, is particularly effective. In the case of adhesives, the compounds of the invention have properties that allow their use in two-component and particularly in single-component systems. The use of the compounds of the invention as built-in adhesive agents in the substrates makes it superfluous to pre-treat the surfaces to be glued with a 12 mm primer.

The substrate is a moisture-hardening polyurethane, and the main constituent is polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethane polyurethaneurethane polyurethaneurethane polyurethaneurethaneurethaneurethaneurethaneurethaneurethaneurethaneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneuraneur

In a preferred embodiment of the invention, polyurethane prepolymers are used instead of multifunctional isocyanate compounds. Prepolymers are the adducts of an excess of multifunctional isocyanate to multifunctional alcohols, such as the products of conversion of one of the above aromatic or aliphatic diisocyanates with ethylene glycol, propylene glycol, glycerin, trimethylolpropane or pentaerythritol. Transformations of diisocyanates with polyether polyols, e.g. polyethylene based on polypropylene oxide or polyether based on polyethylene oxide, are also understood.

Polyester polyols can also be used instead of polyether polyols. Suitable polyester polyols are conversion products of multifunction acids with multifunctional alcohols, for example polyester based on aliphatic and/or aromatic dicarboxylic acid and multifunctional alcohols of functionality 2-4. For example, polyester of acetic acid, sebasic acid, phthalic acid, hydrophthallic acid and/or trimethyl acid on the one hand and ethylene glycol, propylene glycol, neopentyl glycol, hexanglycol, glycerol and/or trimethyl propanol on the other hand can be used. In particular, polyester polyols with a molecular weight (in number) between 5000 and 2000 and, in particular, between 600 and 2000 polyester polyols, can be used as a conversion product of ethylene glycol, propylene glycol, neopentyl glycol, hexanglycol, glycerol and/or trimethyl propanol, for example, with a functional weight of 1 to 2 molybdenol caps, and polyester polyester polyester polyols with aol polyester polyester polyester polyol.

Another suitable class of multifunctional alcohols are polybutadienoles, which are oligomers based on butadiene with OH-groups as end-groups. Products in the molecular weight range 200-4000, especially 500-3000, are suitable.

In the production of polyurethane prepolymers, the ratio of OH groups of the alcohol component to isocyanate groups is important, which is generally between 1:2 and 1:10.

Err1:Expecting ',' delimiter: line 1 column 331 (char 330)

The polyurethane preparations of the invention may also contain various auxiliary substances. For example, fillers may be used. The fillers are inorganic compounds that are not reactive to isocyanates, such as chalk or lime flour, precipitated and/or pyrogenic silica acids, zeolites, bentonites, ground minerals and other inorganic fillers known to the professional, in particular fiber shortcuts and others. For some applications, fillers that give the preparations thixotropy are preferred, for example, flammable plastics, in particular PVC.

In addition to the above compounds, the polyurethane preparations of the invention may contain other auxiliary substances, such as solvents. Solvents which do not react with isocyanate groups are suitable, such as halogenated hydrocarbons, esters, ketones, aromatic hydrocarbons, etc. The use of plasticizers, flame retardants, retardants, dyes and anti-aging agents, as known in polyurethane adhesives and sealants, is also possible.

For some applications it is desirable to add foam stabilizers to the polyurethane preparations of the invention. So-called silicotensin-containing compounds, such as tri-resylphosphates, diphenylcresylphosphates, T-2-chloromethylphosphate, di-resylphosphates, and di-propyl-propyl-3-dipropyl-phosphate, are also commonly used. Additives such as ammonium nitrate, halogenated phosphate, and di-propyl-phosphate can also be used as long-acting agents.

Other possible additives are basic accelerators. Basic accelerators include, for example, tertiary bases such as bis- ((N,N'-dimethylamino) -diethylether, dimethylamino-cyclohexane, N,N-dimethylbenzylamine, N-methylmorpholine, and the conversion products of dialkyl-β-hydroxyethyl-amine with monoisocyanates and esterification products of dialkyl-β-hydroxyethyl-amine and dicarboxylic acids. Another important accelerator is the 1,4-dimethylamino-bicyclo-dioxane.

Polyurethane prepolymers are added to formula I compounds in amounts of 0,1 to 20% by weight, preferably 0,5 to 5% by weight, in particular 0,5-2,5 by weight, depending on the prepolymer.

If formula I compounds are used as hardeners, the molar ratio of released NH groups to free isocyanate groups in the prepolymer should be 0,5 to 1,5:1; preferably 0,9 to 1,1:1.

Manufacture from materials of any heading The following is the list of active substances:

The compound is produced in the manner described in US Patent No. 4.404.379. The water temperature is maintained at a constant temperature of approximately 10 °C. The test chemical is used to determine the concentration of the active substance in the test chemical. The following substances are to be used:

The following table shows the data for the determination of the concentration of the active substance in the feed additive:

The compound is produced in the manner described in US Patent No. 4.404.379. The following shall be added to the list of active substances: The mean value of the sampling intervals for the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of samples of the samples of the samples of the samples of the samples of samples of the samples of the samples of the samples of samples of the samples of the samples of samples of the samples of samples of the samples of samples of samples of samples of the samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of The following is a list of the active substances that may be used in the active substance: Other

The test chemical is used to determine the concentration of the active substance in the test chemical.

The compound is produced in the manner described in EP-A 70536. The water temperature shall be at least: The following is a list of the active substances that may be used in the manufacture of the active substance:

The following is the list of active substances:

The solution of 590 g (6 mol) cyclohexanone is dripped into 400 ml of cyclohexan, 52,8 g (6 mol) 3-methylaminopropylamine is then heated in a nitrogen atmosphere at a water separator to return to flow until approximately 100 ml of water has been removed (10 h). The solvent is then removed at reduced pressure and the residue is fractionated to obtain 680 g 1-methyl-2-pentamethylene-hexahydropyrimidine. The following shall be added to the list of active substances: The following is a list of the active substances that may be used in the manufacture of the active substance: Other

Add 32.3 g (0.45 mol) of isobutyraldehyde to a solution of 100 g (0.45 mol) 3- ((2-aminoethylamino) propyltrimethoxysilan in 200 ml of dry cyclohexane and then heat the solution to return to a water separator until 20 ml of water has been removed (10 h).

The solvent is then removed under reduced pressure and the residue is fractionally distilled to obtain 16 g 1-[3-trimethoxysilyl) propyl]-2-[1-methylethyl) imidazolidine.

The mean value of the test chemical is calculated as the sum of the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical and the mean values of the test chemical. The total number of patients with a history of renal failure was approximately 58,031 in the first year of treatment. Other

The procedure is as in example E, but 44.1 g (0.45 mol) of cyclohexanone is added and 18 ml of water is removed (12 h) to obtain 120 g of product.1 The test chemical is used to determine the concentration of the active substance in the test chemical. The total number of samples of the active substance is estimated at approximately 10 mg/kg. Other The proportion of open structure is calculated by integrating the two methoxy peaks at 3.43 and 3.57 ppm. A tautomerism between two similar structures is mentioned by C. Chapuis et al., Bull. Soc. Chim. Fr. 1973, 977.

Add 75,0 g (0,87 mol) of pivalaldehyde to a solution of 76,7 g (0.87 mol) 3-methylaminopropylamine in 200 ml of dry cyclohexane. After addition, heat the solution to return to a water separator for 3 h. Then remove the solvent in a rotary evaporator and distill the residue. The test chemical is used to determine the concentration of the active substance in the feed additive. The total number of samples of the test chemical is calculated by dividing the total number of samples of the test chemical by the total number of samples of the test chemical. Other

Example H:

A mixture of 150 g (0,714 mol) of freshly distilled 1,6-diisocyanate-2,2,4-trimethylhexane and 140,2 g (0,714 mol) of 3-mercaptopropyltrimethoxylan is heated to 140 °C for 2 h under nitrogen atmosphere to obtain 275,2 g of the product as a colourless liquid with the following analytical data:

The viscosity (according to Epp law): η25 = 380 mPa·s The test chemical is used to determine the concentration of the active substance in the test chemical. The following substances are to be classified as 'metals' in the Annex to Regulation (EC) No 1272/2008 of the European Parliament and of the Council: Other

Example 1:

A mixture of 143.5 g (0.642 mol) isophorondiisocyanate and 126.0 g (0.642 mol) 3-mercaptopropyltrimethoxysilan is heated at 140 °C for 6 hours under nitrogen atmosphere. Then cooled to room temperature, a solution of 90.8 g (0.642 mol) 1-methyl-2-methylethyl-1-hexahydropyrimidine is dripped into 200 ml of dry toluene so that the temperature does not rise above 35 °C. Then stirred at room temperature for 30 minutes and then withdrawn at 100 °C/0.1 on the rotary evaporator. 351 g mbar of the product is obtained with the following analytical data.

Melting point 40 to 50 °C The test chemical is a mixture of the following compounds: α-H-NMR (CDCl3, selected signals): δ 7,55 (d, J = 5 Hz, CH = N); 6,02 - 5,08 (br, m, N-CO-NH + S-CO-NH); 3,56 (s, OCH3); 2,88 (s, N-CH3); 2,41 (qd, J = 10 Hz, 6 Hz, (CH3) 2CH). Other

Example 2:

A solution of 34.4 g (0.14 mol) isocyanatopropyltriethoxysilan in 50 ml of dry toluene is dripped to a solution of 20.0 g (0.142 mol) 1-methyl-2- ((1-methylethyl) hexahydropyrimidine in 50 ml of dry toluene, maintained below 35°C. After completion of the addition, stir the mixture at room temperature for 7 h. Then, at 100°C/0.1 mbar, withdraw the solvent from the rotary evaporator to obtain 50 g of a colourless liquid with the following analytical data:

The mean value of the sampling intervals for the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of the samples of samples of the samples of the samples of the samples of samples of the samples of samples of samples of the samples of samples of samples of the samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samples of samp The following are the active substances which may be used in the manufacture of the active substance: Other

Example 3:

Heat a mixture of 150 g (0.714 mol) of freshly distilled 1,6-diisocyanate-2,2,4-trimethylhexane and 140,2 g (0.714 mol) 3-mercaptopropyltrimethoxylan to 140 °C for 2 h under a nitrogen atmosphere, then cool to room temperature and add a solution of 100,8 g (0.714 mol) 1-methyl-2-(1-methylethyl) hexahydropyrimidine to 200 ml of dry toluene to maintain the temperature below 35 °C. Then stir the mixture at room temperature for another 45 minutes and then remove the solvent at 100 °C/0,1 mbar at evaporation.

The viscosity (according to Epp law): η25= 19200 mPa·s The test chemical is used to determine the concentration of the test chemical in the test chemical. The following substances are to be classified as substances with a specific chemical composition, in accordance with the provisions of Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 16 December 2006 on the approximation of the laws of the Member States relating to the permissible sound power level of compressed air (OJ L 347, 20.12.2006, p. Other

Example 4:

Heat a mixture of 50 g (0.257 mol NCO) of partially trimerised hexamethylenediisocyanate with an isocyanate content of 21.6% (Desmodur® N 3200 of Bayer AG) and 33.7 g (0.171 mol) 3-mercaptopropyltrimethoxylan at 140°C for 60 minutes. Cool to room temperature and then drip a solution of 12.2 g (0.0857 mol) 1-methyl-3-methylethyl) hexahydropyrimidine into 100 ml of dry toluene to maintain the temperature below 35°C. Then stir the mixture at room temperature for 10 h and then vaporize the solvent at 100°C/0.1 mbar. The resulting product is obtained as a viscous analytical product with the following analytical data.

The viscosity (according to Epp law): η80 = 66500 mPa·s The test chemical is used to determine the concentration of the active substance in the test chemical and to determine the concentration of the active substance in the test chemical. Other

Example 5:

The procedure is as in example 4: 50 g (0.257 mol NCO) of partially trimered hexamethylenediisocyanate with an isocyanate content of 21.6% (Desmodur® N 3200 of Bayer AG), 16.8 g (0.0857 mol) of 3-mercaptopropyltrimethoxylan and 24.4 g (0.171 mol) of 1-methyl-2-methylethyl) hexahydropyrimidine are used, resulting in a viscous material with the following analytical data:

The viscosity (according to Epp law): η80= 56300 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. The following substances are to be classified as substances with a specific chemical composition, in accordance with the provisions of Regulation (EC) No 1907/2006, as defined in the Annex to this Regulation: Other

Example 6:

The procedure is as in example 4: 50 g (0.255 mol NCO) of biorethyl partially hydrolysed hexamethylenediisocyanate with an isocyanate content of 21,3% (Desmodur® N 100 from Bayer AG), 33.5 g (0.17 mol) 3-mercaptopropyltrimethoxylan and 12 g (0.085 mol) 1-methyl-2-(1-methylethyl) hexahydropyrimidine are applied, resulting in a viscous product with the following analytical data:

The viscosity (according to Epp law): η40= 88320 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. Other

Example 7:

A solution of 50 g (0.257 mol) of partially trimered hexamethylenediisocyanate with an isocyanate content of 21.6% (Desmodur® N 3200 from Bayer AG) in 50 ml of dry toluene is placed in a vessel with a mechanical agitator, a drip funnel and a thermometer, placed under a nitrogen atmosphere and immersed in an ice bath. A solution of 30.6 g (0.171 mol) of 3-aminopropyltrimethoxylanate is then dripped in dry toluene. An exothermic reaction is immediately initiated; the drip rate is set to keep the temperature below 30°C. After the mixture is added, the mixture is raised to 1 mA room temperature and cooled down to 1 mA (100°C) while the product is cooled down to 1 mA (10.085-1 mA). The product is then cooled to 1 mA (10.080-1 mA) room temperature and cooled to 1 mA (10.080-1 mA) with the following method of analysis:

The viscosity (according to Epp law): η80= 39040 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. Other

Example 8:

A mixture of 50 g (0.257 mol NCO) of partially trimerised hexamethylenediisocyanate with an isocyanate content of 21.6% (Desmodur® N 3200 of Bayer AG) and 16.8 g (0.0857 mol) 3-mercaptopropyltrimethoxylan is heated at 140°C for 60 minutes and then cooled to room temperature. A solution of 15.3 g (0.0857 mol) 3-aminopropyltrimethoxylan is then dripped into 50 ml of dry toluene to keep the temperature below 35°C. After completion of the addition, the mixture is viscously stirred at room temperature for 2 hours. A solution of 12.085 g (0.0857 ml) 1-methyl-2-methylmethyltrimethoxylamide is then stirred into 100 ml of the test chemical to obtain a solution of 100 mbar (1,2 ml) of T-methylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethyl

The viscosity (according to Epprecht): η80= 102 400 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. Other

Example 9:

The following procedure is used in example 4: 200 g (1,028 mol NCO) of partially trimered hexamethylenediisocyanate with an isocyanate content of 21,6% (Desmodur® N3200 from Bayer AG), 134,8 g (0,684 mol) of 3-mercaptopropyltrimethoxylan and 53,7 g (0,343 mol) of N-methyl-3- ((2,2-dimethylpropylimino) propylamine.

The viscosity (according to Epprecht): η80= 6080 mPa·s The test chemical is used to determine the concentration of the active substance in the test chemical and to determine the concentration of the active substance in the test chemical.

Example 10:

A solution of 23,8 g (0.096 mol) of isocyanatopropyltriethoxysilan in 30 ml of dry toluene is dripped to a solution of 15 g (0.096 mol) N-methyl-3-(2,2-dimethylpropylimino) propylamine in 20 ml of dry toluene and stirred at room temperature for 1 h. The solvent is then withdrawn at 90 °C/0,1 mbar in the rotary evaporator to obtain 35,7 g of colourless liquid with the following analytical data:

The viscosity (according to Epprecht): η25= 120 mPa·s The total number of doses administered to the controlled animals was approximately 10 mg/kg/kg/kg, with a mean of 0,05 mg/kg/kg/kg/kg/kg. Other

Example 11:

The procedure is as in example 4: 50 g (0.257 mol NCO) of partially trimerised hexamethylenediisocyanate with an isocyanate content of 21,6% (Desmodur® N 3200 of Bayer AG), 33.7 g (0.171 mol) 3 mercaptopropyltrimethoxy silane and 8.6 g (0.0857 mol) 1-methylhexahydropyrimidine are applied, resulting in a product with the following analytical data:

The viscosity (according to Epp law): η80= 28160 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. The test chemical is used to determine the concentration of the active substance in the test chemical. Other

Example 12

A solution of 3 g (0.018 mol) of hexmethyllendiisocyanate in 50 ml of dry toluene is dripped by stirring to a solution of 10 g (0.036) 1-[3-trimethoxysilyl) propyl]-2-(1-methylethyl) imidazolidine in 50 ml of dry toluene, stirred for 2 h and then withdrawn at 90 °C/0.1 mbar in the rotary evaporator to obtain 13 g of viscous material of the above structure2 and the following analytical data: Approximately 15% of the open structure can be detected by 1H-NMR. Other The viscosity (according to Epp law): η25= 80250 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. Other

Example 13:

A solution of 5 g (0.018 mol) 1-[3-[trimethoxysilyl) propyl]-2-(1-methylethyl) imidazolidine in 50 ml of dry toluene is dripped by stirring to a solution of 8.1 g (0.018 mol) of the product of example H in 50 ml of dry toluene, stirred at room temperature for 24 h and then withdrawn at 95°C/0,1 mbar on the rotary evaporator to obtain 13 g of the product of the above structure3 and the following analytical data: The viscosity (according to Epp law): η25= 68200 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. Other Approximately 15% of the open structure can be detected by 1H-NMR (analogue, e.g. 12).

Example 14:

A solution of 15,0 g (0.054 mol) 1-[3-[trimethoxysilyl) propyl]-2-[1-methylethyl) imidazolidine in 30 ml of dry toluene is agitated to a solution of 13,4 g (0.054 mol) isocyanatopropyl triethoxysilan in 30 ml of dry toluene and further stirred at room temperature for 3 h. The solvent is then diluted at 95°C/0,1 mbar on the rotary evaporator to obtain 27 g of the product of the above structure4 and the following analytical data: The method of analysis is based on the following equation: the viscosity (according to Epprecht): η25= 1952 mPa·s 1H-NMR (CDCl3): δ 4,47 (br, N-CO-NH); 4,27 (d, J = 6,4 Hz, N-CH-N); 3,81 (q, J = 7,0 Hz, 0CH2); 3,56 (s, OCH3); 3,34 - 2,82 (m, 8 H); 2,54 - 2,15 (m, 2 H); 1,91 - 1,56 (m, 3 H); 1,22 (t, J = 7,0 Hz, OCH2-CH3); 1,02 - 0,89 (m, C(CH3)); 0,71 - 0,55 (m, CH2-Si). The total number of patients with a history of renal failure was approximately 10 in the population. Other 4 20 % of the open structure can be detected by 1H-NMR (analogue, e.g. 12)

Example 15

A solution of 13 g (0.044 mol) 1-[3-trimethoxysilyl) propyl]-2-pentamethylene-imidazolidine in 100 ml of dry toluene is dripped by stirring to a solution of 20 g (0.044 mol) of the product of sample H in 100 ml of dry toluene, stirred at room temperature for 2 h and then withdrawn at 95 °C/0,1 mbar in the rotary evaporator to obtain a product of the above structure5 and the following analytical data: The viscosity (according to Epp law): η25= 76800 mPa·s Other 5 The open structure (analogue to example 12) can also be demonstrated.

Example 16:

A solution of 15 g (0.049 mol) 1-[3- ((trimethoxysilyl) propyl) 2-pentamethylene-imidazolidine in 30 ml of dry toluene is dripped by stirring to a solution of 12.3 g (0.049 mol) isocyanatopropyl triethoxysilan in 30 ml of dry toluene, stirred at room temperature for 3 h and then drained at 95°C/0.1 mbar in a rotary evaporator to obtain 27 g of the product of the above structure6 and the following analytical data: The viscosity (according to Epp law): η25= 2400 mPa·s Other 6 The open structure (analogue to example 12) can also be demonstrated.

Example 17:

Heat a mixture of 72,4 g (0.326 mol) isophorondiisocyanate and 64,0 g (0.326 mol) 3-mercaptopropyltrimethoxylan to 140 °C for 60 minutes, allow it to cool to room temperature and then slowly add a solution of 54,8 g (0.326 mol) 1-methyl-2-pentamethylene-hexahydropyrimidine to keep the temperature below 35 °C. Stir for 30 minutes and then withdraw the solvent at 100 °C/0,1 mbar on the rotary evaporator to obtain 188,6 g of the product with the following data: The melting point is 40°C. Other

Example 18:

A solution of 28,7 g (0.116 mol) of isocyanatopropyltriethoxysilan in 50 ml of dry toluene is dripped to a solution of 20,0 g (0.119 mol) 1-methyl-2-pentamethylene-hexahydropyrimidine in 50 ml of dry toluene, so that the temperature is kept below 35°C. After completion of the addition, stir at room temperature for 7 h, withdraw the solvent at 100°C/0,1 mbar on the rotary evaporator to obtain 46,8 g of a yellow liquid with the following analytical data: The viscosity (according to Epprecht): η25= 80 mPa·s The total number of patients with a history of renal failure was approximately 104, with a mean of the total number of patients with renal failure of less than 1%. Other

Example 19:

A mixture of 150 g (0.714 mol) of freshly distilled 1,6-diisocyanate-2,2,4-trimethylhexane and 140 g (0.714 mol) 3-mercaptopropyltrimethoxylan is heated to 140 °C for 2 h under a nitrogen atmosphere and then cooled to room temperature. A solution of 120 g (0.714 mol) 1-methyl-2-pentamethylene-hexahydropyrimidine is then dripped into 200 ml of dry toluene to maintain the temperature below 35 °C. After completion of the addition, the mixture is further stirred at room temperature for 45 minutes, after which the solvent is removed at 100 °C/0,1 mbar at rotation and 380 g of the analyte is obtained with the following analytical results: The melting point is 35°C. Other

Example 20:

A solution of 24,7 g (0.0998 mol) isocyanatopropyltriethoxysilan in 30 ml of dry toluene is dripped to form a solution of 10,0 g (0.0998 mol) 1-methylhexahydropyrimidine in 30 ml of dry toluene, stirred at room temperature for 2 h, and then withdrawn at 90 °C/0,1 mbar in the rotary evaporator to obtain 24,2 g of colourless liquid with the following analytical data. The viscosity (according to Epp law): η25= 400 mPa·s The following substances are considered to be toxic if they are used in the manufacture of the active substance: The total number of patients with a history of renal failure was approximately 10 in the population. Other

Example 21:

A solution of 4,86 g (0.0196 mol) isocyanatopropyltriethoxysilan in 30 ml of dry toluene is dripped to a solution of 3,6 g (0.0196 mol) 1- ((2-hydroxyethyl) -3- ((2-cyanoethyl) -hexahydropyrimidine in 30 ml of dry toluene at 100 °C, stirred for 1.5 h at 100 °C, and then withdrawn at 90 °C/0,1 mbar at the rotary evaporator to obtain 8,2 g of a colourless liquid with the following analytical data: The viscosity (according to Epp law): η25 = 440 mPa·s The following substances are to be classified as 'metals' and 'metals' in the Annex to Regulation (EC) No 1272/2008 of the European Parliament and of the Council. The total number of patients with a history of renal failure was approximately 104, with a mean of 13C-NMR (CDCl3): δ 155.8; 118.4; 74.4; 61.6; 57.7; 53.0; 51.9; 51.4; 49.4; 42.9; 22.8; 22.0; 17.8; 16.1; 7.1. Other

Example 22:

Heat a mixture of 15.9 g (0.08 mol NCO) of partially trimerised hexamethylendiisocyanate with an isocyanate content of 21.6% (Desmodur® N 3200 of Bayer AG) and 10.7 g (0.054 mol) 3-mercaptopropyltrimethoxylan at 140°C for 60 minutes, cool to 100°C, add 5.0 g 1-(2-hydroxyethyl) -3-(2-cyanoethyl) hexahydropyrimidine, stir at the same temperature for 5 h. Evaporate the solvent at 95°C/0.1 h at the rotational mbar ferrite and obtain the following product analysis: The viscosity (according to Epprecht): η80= 7680 mPa·s The test chemical is used to determine the concentration of the test chemical in the test medium. The test chemical is used to determine the concentration of the test chemical in the test medium. The following are to be considered as components of the product: The following substances are to be classified in the same heading as the product: Other

Example 23: A) Prepolymer synthesis:

An isocyanated prepolymer is prepared by infusing a mixture of 531 g of dry bishydroxyl terminated polypropylene glycol of molecular weight 2000 (Desmophen® 1900U of Bayer AG) and 0.3 ml of dibutyltin dihydrate at 80°C with 150 g of methylphenyldiisocyanate (Isonate® M125 of Upjohn) and 0.3 ml of dibutyltin dihydrate, then mixing with 2.7 g of trimethylolopan and stirring for another 2 hours at 80°C until an isocyanated prepolymer with an isocyanate content of 2.4% has been formed.

B) Liability for glass

The results are summarised in Table 1, where (-) means that the layer can be easily removed and the glass surface is kept clean; (-) means that the layer can be easily removed and the glass surface remains clean; (+/-) means that most of the layer on the glass surface can be removed by scratching with a scraper; (+) means that most of the layer remains on the glass surface despite scratching; (+) means that most of the layer remains on the glass surface despite scratching; (+) means that most of the layer remains on the glass surface despite scratching; (+) means that the glass surface remains on the glass surface despite scratching. Other

Claims

A compound of general formula I wherein R¹ is C₂-C₃alkylene, R² is hydrogen, unsubstituted C₁-C₆alkyl or C₁-C₆alkyl substituted by -OH, -CN or by -Si(OR³)_3-qR⁴q, or C₂-C₆-alkenyl, R³ is C₁-C₄alkyl, or two radicals R³ together are C₁-C₄alkylene, R⁴ is C₁-C₄alkyl or phenyl, and q is from 0 to 2, and E is a radical of the formula wherein R⁵ is hydrogen or C₁-C₄alkyl and R⁶ is hydrogen, or R⁵ and R⁶ together are C₄-C₈alkylene, or E together with R² is a radical of the formula wherein R⁷ is hydrogen, C₁-C₄alkyl or -R⁹-Si(OR³)_3-qR⁴_q, wherein R³, R⁴ and q are as defined above and R⁹ is C₁-C₈alkylene, and R⁸ is a radical wherein R¹⁰ is hydrogen or C₁-C₄alkyl and R¹¹ is hydrogen, or R¹⁰ and R¹¹ together are C₄-C₈alkylene, and A is ⁅(CH₂)_r-O⁆, wherein r is 1, 2 or 3, and p is 0 or 1, and Y is oxygen or sulfur; and wherein T is a radical R⁹-Si(OR³)_3-qR⁴_q, a radical of the formula or, when R⁷ is a radical of the formula -R⁹-Si(OR³)_3-qR⁴_q and m is ≧ 2, T is an m-valent radical Z, wherein R³, R⁴ R⁹, Y and q are as defined above, X is -S- or -NH-, and Z is an organic radical derived from a polyisocyanate or polyisothiocyanate having at least two NCO or NCS groups, respectively, and m is ≧ 1, and n is ≧ 1.
A compound according to claim 1 wherein Y is O.
A compound according to claim 1 of formula l, wherein Z is derived from an aliphatic, cycloaliphatic, aliphatic/aromatic, aromatic or heterocyclic polyisocyanate or polyisothiocyanate having ≧ 2 NCO or NCS groups, this radical optionally containing one or more ester, ether, urethane, thiourethane, isocyanurate, urea or biuret functions.
A compound according to claim 3 of formula I, wherein Z is derived from an aliphatic or mixed aliphatic/aromatic polyisocyanate having ≧ 2 NCO groups, this radical Z optionally containing one or two ester, ether, urethane, thiourethane, isocyanurate, urea or biuret functions.
A compound according to claim 1 of formula I, wherein the radical Z has a mean molecular weight M_n < 10 000.
A compound according to claim 1 of formula I, wherein n and m each independently of the other are from 1 to 49.
A compound according to claim 1 of formula I, wherein the sum of n + m is from 2 to 50.
A compound according to claim 1 of formula I, wherein n is 1, 2 or 3 and m is 3, 2 or 1.
A compound according to claim 1 of formula I, wherein E together with R² is a radical of the formula and R¹ is ethylene.
A compound according to claim 1 of formula I, wherein p is 0.
A compound according to claim 1 of formula I, wherein q is 0.
A compound according to claim 1 of formula I, wherein E is a radical of the formula
A compound according to claim 12 of formula I, wherein R⁵ is isopropyl or tert-butyl or R⁵ together with R⁶ is tetramethylene or pentamethylene.
A compound according to claim 1 of formula I, wherein T is a radical of the formula -R⁹-Si(OR³)_3-qR⁴_q or
A compound according to claim 14 of formula I, wherein at least one radical X is -S-.
A compound according to claim 1 of formula I, wherein p is O and m is 1, E is a radical wherein R⁵ is C₃- or C₄-alkyl, and R² is C₁-C₄alkyl.
A moisture-curing polyurethane resin comprising at least one compound of formula I according to claim 1.
A resin according to claim 17 comprising from 0.1 to 20 % by weight of a compound of formula I.