阅读说明：本技术 用于湿固化组合物的干燥剂 (Desiccant for moisture-curing compositions ) 是由 C·蒂贝斯 F·J·施滕普弗莱 K·洛伦茨 U·纳特克 于 2019-08-14 设计创作，主要内容包括：本发明涉及可通过如下制备的聚合物组合物：(a)使每分子具有恰好一个NCO反应性基团的NCO反应性聚合物与二异氰酸酯反应,其中二异氰酸酯分子与NCO反应性聚合物的NCO反应性基团的摩尔比为至少2:1；和(b)使得自步骤a)的反应产物中剩余的NCO基团与NCO反应性硅烷反应。本发明还涉及包含所述聚合物组合物的水分反应性组合物以及制备所述聚合物组合物和包含该聚合物组合物的水分反应性组合物的方法。本发明最后涉及所述聚合物组合物作为用于湿固化的粘合剂、密封剂和涂料的干燥剂的用途。(The present invention relates to a polymer composition which can be prepared by: (a) reacting an NCO-reactive polymer having exactly one NCO-reactive group per molecule with a diisocyanate, wherein the molar ratio of diisocyanate molecules to NCO-reactive groups of the NCO-reactive polymer is at least 2: 1; and (b) reacting the NCO groups remaining from the reaction product of step a) with an NCO-reactive silane. The invention also relates to moisture-reactive compositions comprising the polymer composition and to processes for preparing the polymer composition and moisture-reactive compositions comprising the polymer composition. The invention finally relates to the use of the polymer composition as a drying agent for moisture-curing adhesives, sealants and coatings.)

1. A polymer composition preparable by:

a) reacting an NCO-reactive polymer having a molecular weight Mn of 2000 to 25000 g/mol having exactly one NCO-reactive group per molecule with a diisocyanate, wherein the molar ratio of diisocyanate molecules to NCO-reactive groups of the NCO-reactive polymer is at least 2: 1;

and then subsequently

b) Reacting the NCO groups remaining in the reaction product from step a) with an NCO-reactive silane.

2. The polymer composition according to claim 1, wherein in step a) the molar ratio of diisocyanate to NCO-reactive groups of the NCO-reactive polymer is from 2:1 to 20: 1.

3. The polymer composition of any one of claims 1 and 2, wherein the number average molecular weight of the NCO-reactive polymer is 2000 to 25000 g/mol.

4. The polymer composition of any one of claims 1 to 3, wherein the NCO reactive polymer is a monohydric alcohol.

5. The polymer composition according to any one of claims 1 to 4, wherein the diisocyanate is selected from the group consisting of polyisocyanates of the following group: 1, 4-diisocyanatobutane (BDI), 1, 5-diisocyanatopentane (PDI), 1, 6-Hexamethylene Diisocyanate (HDI), 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethylpentane, 2, 4-or 2,4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, 1, 3-and 1, 4-diisocyanatocyclohexane, 1, 4-diisocyanato-3, 3, 5-trimethylcyclohexane, 1, 3-diisocyanato-2-methylcyclohexane, 1, 3-diisocyanato-4-methylcyclohexane, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4 '-and 4,4' -diisocyanatodicyclohexylmethane (H12MDI), 1, 3-and 1, 4-bis (isocyanatomethyl) cyclohexane, bis (isocyanatomethyl) Norbornane (NBDI), 4 '-diisocyanato-3, 3' -dimethyldicyclohexylmethane, 4 '-diisocyanato-3, 3',5,5 '-tetramethyldicyclohexylmethane, 4' -diisocyanato-1, 1 '-bis (cyclohexyl), 4' -diisocyanato-3, 3 '-dimethyl-1, 1' -bis (cyclohexyl), 4 '-diisocyanato-2, 2',5,5 '-tetramethyl-1, 1' -bis (cyclohexyl), 1, 8-diisocyanato-p-menthane, 1, 3-diisocyanato-adamantane, 1, 3-dimethyl-5, 7-diisocyanato-adamantane, 1, 3-and 1, 4-bis (isocyanatomethyl) benzene (xylylene diisocyanate; XDI), 1, 3-and 1, 4-bis (1-isocyanato-1-methylethyl) benzene (XDTMI), bis (4- (1-isocyanato-1-methylethyl) phenyl) carbonate, 2, 4-and 2, 6-diisocyanatotoluene (TDI), 2,4 '-and 4,4' -diisocyanatodiphenylmethane (MDI), 1, 5-diisocyanatonaphthalene and mixtures thereof.

6. The polymer composition of any one of claims 1 to 5, wherein the NCO-reactive silane is a compound of formula (I):

R¹ ₃Si(CH₂)_nX (I),

wherein

R¹Each radical being independently of the others selected from C₁-C₈-alkyl radical, C₆-C₂₀-aryl radical, C₁-C₈-alkoxy or C₁-C₈-acyloxy, and the radical R¹Is at least one of C₁-C₈-alkoxy or C₁-C₈-an acyloxy group,

n is an integer of 1 to 4,

x is selected from-OH, -SH or-NHR²；

R²Is selected from H, C₁-C₂₀-alkyl, -CH₂CH₂CN or-CHR³CH₂COOR⁴，

R³Selected from H and-COOR⁴And are and

R⁴each is C₁-C₂₀-an alkyl group.

7. A process for preparing a polymer composition according to any one of claims 1 to 6, comprising the steps of:

a) reacting an NCO-reactive polymer having at least two NCO-reactive groups with a diisocyanate, wherein the molar ratio of NCO-reactive groups of the diisocyanate to the NCO-reactive polymer is at least 1.25; and

b) reacting the reaction product from step a) with an NCO-reactive silane.

8. Moisture-curing composition comprising the polymer composition according to any one of claims 1 to 6 and at least one additive selected from the group consisting of: one or more fillers, one or more crosslinking catalysts, one or more tackifiers and/or one or more plasticizers.

9. The moisture-curable composition of claim 8, wherein the moisture-curable composition has a water content of at most 0.1 weight percent, based on the total weight of the moisture-curable composition, determined according to DIN EN ISO 15512:2017-03, method B2.

10. The moisture-curable composition according to any one of claims 8 and 9, which does not comprise an additional desiccant.

11. The moisture-curable composition of any one of claims 8 and 9, comprising less than 1 wt% of a vinyl-containing silane, based on the total weight of the moisture-curable composition.

12. The moisture-curable composition according to any one of claims 8 to 11, comprising

5 to 50 weight percent of the polymer composition of claims 1 to 6;

10 to 70 weight percent of at least one filler;

up to 5 wt% of at least one tackifier;

0.001 to 5 wt% of at least one crosslinking catalyst; and

up to 50% by weight of at least one plasticizer,

each based on the total weight of the moisture-curable composition.

13. A method of preparing the moisture-curable composition of any one of claims 8 to 12 by: mixing the polymer composition according to any one of claims 1 to 6 with at least one filler, at least one tackifier, at least one crosslinking catalyst and/or at least one plasticizer.

14. The process according to claim 13, wherein the polymer composition according to any one of claims 1 to 6 is mixed with at least one filler having a water content of at most 1% by weight, based on the total weight of filler.

15. The method of any one of claims 12 and 13, wherein up to 1 wt% of a vinyl-containing silane is added to the moisture-curing composition.

16. Use of the polymer composition according to any one of claims 1 to 6 as a desiccant for moisture-curing adhesives, sealants and coatings.

17. Parquet adhesive comprising the polymer composition according to any of claims 1 to 6.

Examples

To prepare the polymer compositions according to the invention, the following polyoxypropylene polymers having in each case one hydroxyl group per molecule, starting with diethylene glycol monobutyl ether, prepared analogously to the procedure in EP 0654302 a1, were used.

Monohydric alcohols I

OH number C55.1 mg KOH/g (determined according to DIN 53240-1(2012), molar mass corresponding to 1018 g/mol)

Viscosity at 25 ℃ 80 mPas

Water content 100 ppm

Monohydric alcohol II

OH number 12.7 mg KOH/g (determined according to DIN 53240-1(2012), molar mass corresponding to 4417 g/mol)

Viscosity at 25 ℃ 814 mPas

Water content 100 ppm

Monool III

OH number 2.9 mg KOH/g (determined according to DIN 53240-1(2012), molar mass corresponding to 19345 g/mol)

Viscosity at 25 ℃ 36100 mPas

The water content was 200 ppm.

Preparation of aspartate AE1

Diethyl N- (3-trimethoxysilylpropyl) aspartate is prepared according to EP-A0596360, example 5.

Preparation of silane-functional Polymer SP

In a2 l sulfonation beaker with lid, stirrer, thermometer and nitrogen flow through, 880.1g of propylene glycol (Acclaim Polyol 8200N, Covestro Deutschland AG; Leverkusen DE) having an OH number of 13.4 mg KOH/g (determined according to DIN 53240-1 (2012)) and 46.7g of isophorone diisocyanate (IPDI, Desmodur)^®I, Covestro Deutschland AG, NCO content 37.8%, molar mass 222 g/mol) was reacted at 60 ℃ after addition of 0.04g of dibutyltin dilaurate until the theoretical isocyanate content was reached. Addition of the amount of NCO-reactive silane in Table 1After the amount of diethyl N- (3-trimethoxysilylpropyl) aspartate (prepared according to EP-A0596360, example 5) had been discharged, the mixture was stirred further until no more isocyanate bands could be observed in the IR spectrum.

Preparation of the Polymer composition according to the invention P1-P3

In a2 l sulfonation beaker with lid, stirrer, thermometer and nitrogen flow, the polyoxypropylene polymer in the amounts given under "monool I-III" in Table 1 was reacted with hexamethylene diisocyanate (HDI, Desmodur) in the amounts given under "hexamethylene diisocyanate" in Table 1^®H, Covestro Deutschland AG, NCO content 50%, molar mass 168 g/mol) was reacted at 60 ℃ after addition of dibutyltin dilaurate in the amounts indicated in Table 1 under "dibutyltin dilaurate" until the NCO-reactive groups of the NCO-reactive polymer (here, the hydroxyl groups of the polyoxypropylene polymer) had reacted to completion. After addition of the amount of diethyl N- (3-trimethoxysilylpropyl) aspartate given in Table 1 under "aspartate AE 1", the mixture was stirred further until no more isocyanate band could be observed in the IR spectrum. The viscosity of the resulting polymer composition was determined 24 hours after the preparation of the polymer composition, according to the procedure in DIN EN ISO 3219/B3, using a Physica MCR 51 rheometer from the company Anton Paar Germany GmbH (D).

TABLE 1

Polymer composition	P1	P2	P3
				Monohydric alcohols I	509.0 g
Monohydric alcohol II		421.4 g
				Monool III			831.9 g
Hexamethylene diisocyanate	168.0 g	112.2 g	36.1 g
				Aspartic ester AE1	527.2 g	466.1 g	136.0 g
Dibutyl tin dilaurate	0.06 g	0.05 g	0.05 g
				NCO group equivalent	2	1.33	0.43
OH group equivalent	0.5	0.095	0.043
				Index of refraction	4	14	10
Silane equivalent weight	1.5	1.23	0.387
				Viscosity [ Pas ]]24 h after preparation	1.6	3.0	56

Example FZ-2:

preparation of moisture-curing compositions without addition of vinyl silane

The polymer compositions P1-P3 were mixed with water in the amounts indicated in the table, the mixture was homogenized in a Speedmixer for 10 minutes and the viscosity was measured at 23 ℃ after 24 hours of storage in a closed container.

TABLE 2

Amount of P1 [ g]	Amount of Water [ g ]]	Molar ratio of water/-SiOR3	Viscosity after 24 hours at 23 DEG C
				50	1.68	1:1.3	1.3
50	1.26	1:1	1.2
				50	0.84	1:0.66	1.2
50	0.42	1:0.33	1.2
				Amount of P2 [ g]	Amount of Water [ g ]]	Molar ratio of water/-SiOR3	Viscosity after 24 hours at 23 DEG C
50	1.8	1:1.3	2.6
				50	1.35	1:1	2.5
50	0.9	1:0.66	2.5
				50	0.45	1:0.33	2.4
Amount of P3 [ g]	Amount of Water [ g ]]	Molar ratio of water/-SiOR3	Viscosity after 24 hours at 23 DEG C
				50	0.52	1:1.3	Is viscous
50	0.39	1:1	Is viscous
				50	0.26	1:0.66	64
50	0.13	1:0.33	45

It was shown (see table 2) that polymer composition P1-P3 reacted with stoichiometric and sub-stoichiometric amounts of water and remained liquid to viscous in this case. In this case, the viscosity-increasing effect of increasing the molar mass is at least partly compensated by the viscosity-reducing effect of releasing methanol. Thus, the polymer composition P1-P3 clearly acted as a desiccant.

Example FZ-1 (according to the invention, without the desiccant VTMO)

A moisture-curable composition based on polymer composition P2 was prepared according to the following protocol: 516.16g of a filler Omyalite which had previously been dried in a circulating air drying cabinet at 100 ℃ for 16 hours to a water content of 0.08% by weight^®95T (calcium carbonate, Omya) with 132.2 g of plasticizer (Mesamoll)^®Lanxess Corp, water content 0.03% by weight), 267.21 g of silane-functional polymer SP and 56.2g of polymer composition P2, 8.1 g of Cab-O-Sil^®TS 720 (hydrophobic fumed silica, Cabot, 0.11% by weight water) and 2.9 g of 1, 8-diazabicyclo [ 5.4.0%]Undec-7-ene (Sigma-Aldrich Co. LLC) was dispersed in a laboratory dissolver under static vacuum and cooling with a butterfly stirrer (200 rpm) and a dissolving disk (2500 rpm) for 15 minutes. Static vacuum is understood here to mean that the apparatus is evacuated to a pressure of 200 mbar (dynamic vacuum) and then disconnected from the vacuum pump. The cooling is chosen so that the temperature does not exceed 65 ℃ during the entire preparation. 1.0g of aminopropyltrimethoxysilane (Dynasilan AMMO, Evonik) was then added and the mixture was homogenized for 5 minutes under static vacuum using a butterfly stirrer (200 revolutions per minute).

Example FZ-2 (comparative, FZ-2, but without addition of the Polymer composition P2 according to the invention, without the desiccant VTMO)

Moisture-curing compositions based on amino-functional polymers SP were prepared according to the following protocol: 578.8g of a filler Omyalite which had previously been dried in a circulating air drying cabinet at 100 ℃ for 16 hours to a water content of 0.08% by weight^®95T (calcium carbonate, Omya) with 136.2 g of plasticizer (Mesamoll)^®Lanxess, water content 0.03% by weight), 275.5 g of amino-functional polymer SP, 8.4 g of Cab-O-Sil^®TS 720 (hydrophobic fumed silica, Cabot, 0.11% by weight water) and 3 g of 1, 8-diazabicyclo [ 5.4.0%]Undec-7-ene (Sigma-Aldrich Co. LLC) was dispersed in a laboratory dissolver under static vacuum and cooling with a butterfly stirrer (200 rpm) and a dissolving disk (2500 rpm) for 15 minutes. Static vacuum is understood here to mean that the apparatus is evacuated to a pressure of 200 mbar (dynamic vacuum) and then disconnected from the vacuum pump. The cooling is chosen so that the temperature does not exceed 65 ℃ during the entire preparation. 1.0g of aminopropyltrimethoxysilane (Dynasilan AMMO, Evonik) was then added and the mixture was homogenized for 5 minutes under static vacuum using a butterfly stirrer (200 revolutions per minute).

Example FZ-3 (comparative FZ-1, but without addition of the Polymer composition P2 according to the invention, with a desiccant VTMO and an aminosilane)

Moisture-curing compositions based on amino-functional polymers SP were prepared according to the following protocol: 578.8g of a filler Omyalite which had previously been dried in a circulating air drying cabinet at 100 ℃ for 16 hours to a water content of 0.08% by weight^®95T (calcium carbonate, Omya) with 136.2 g of plasticizer (Mesamoll)^®Lanxess, water content 0.03% by weight), 275.5 g of amino-functional polymer SP, 8.4 g of Cab-O-Sil^®TS 720 (hydrophobic fumed silica, Cabot, 0.11% by weight water) and 1.2 g of 1, 8-diazabicyclo [ 5.4.0%]Undec-7-ene, and 25.0g vinyltrimethoxysilane (Dynasilan VTMO, Evonik) (Sigma-Aldrich Co. LLC) in a laboratory dissolver under static vacuum and cooling, dispersed for 15 minutes using a butterfly stirrer (200 rpm) and a dissolving disk (2500 rpm). Static vacuum is understood here to mean the evacuation of the apparatusTo a pressure of 200 mbar (dynamic vacuum) and then disconnected from the vacuum pump. The cooling is chosen so that the temperature does not exceed 65 ℃ during the entire preparation. 15.0g of oligomeric aminosilane (Dynasilan 1146, Evonik) were then added and the mixture was homogenized for 5 minutes under static vacuum with a butterfly stirrer (200 revolutions per minute).

Determination of viscosity, Shore hardness, elongation at break and tensile Strength

After 7 days of storage in the drum, the moisture-curing composition is applied to the polyethylene film as a film with a uniform layer thickness of 2 mm by means of a spatula and cured at 23 ℃ and 50% air humidity for 14 days, wherein after 7 days the film is peeled off the film and turned over. The properties of these films were subsequently determined by means of the following method.

Unless otherwise stated, the viscosity is determined after seven or sixty days of storage at a shear rate of 40/s according to the procedure in DIN EN ISO 3219/B3.

The Shore A hardness test was carried out on the film according to the procedure in DIN ISO 7619-1. To determine the shore a hardness, three films were laid on top of each other to ensure a layer thickness of 6 mm.

Determination of the elongation at break and tensile strength was carried out by tensile testing according to the procedure in DIN 53504 on an S2 dumbbell punched out of the film prepared as described above with a forming punch. The test speed was 200 mm/min.

Determination of skin formation time

A film of the adhesive was applied by means of a doctor blade (200 μm) to a glass plate previously cleaned with ethyl acetate and immediately placed in a drying recorder (BK 3 drying recorder, BYK-Gardner). The needle was loaded with 10 g and moved a 35cm path over a 24 hour period. The dry recorder was located in a climate chamber at 23 ℃ and 50% relative air humidity. The point at which the permanent trace of the needle disappeared from the film was given as the skin formation time.

Determination of the Water content

The water content was determined in accordance with DIN EN ISO 15512:2017-03, method B2.

Determination of tensile shear Strength

Tensile shear strength was determined according to DIN EN 14293, storage sequence b).

TABLE 3

Moisture-curable composition	FZ-1	FZ-2	FZ-3
						VB	VB
Silane-functional polymers SP [ g ]]	267.2	275.5	275.5
				MESAMOLL® [g]	132.2	136.2	136.2
CAB-O-SIL® TS 720 [g]	8.1	8.4	8.4
				OMYALITE® 95T [g]	516.6	578.8	578.8
DBU [g]	3.0	3.0	1.2
				Dynasilan® VTMO [g]	-	-	25.0
Polymer composition P1 [ g]	56.0	-	-
				Polymer composition P2 [ g]	-	-	-
Dynasilan® 1146 [g]	-	-	15.0
				Dynasilan® AMMO [g]	1.0	1.0
State just after preparation	Paste-like	Paste-like	Paste-like
				State 1 day after preparation	Paste-like	Gelled	Paste-like
State 7 days after preparation	Paste-like	Gelled	Paste-like
				Epidermal formation time after 7 days storage at 23 ℃ [ h]	10	Gelled	60
Epidermal formation time [ h ] after 30 days of storage at 23 ℃]	10	Gelled	60
				Tensile Strength [ N/mm ]2]	1.8	n.b.	2.7
Elongation at break [% ]]	154	n.b.	170
				Shore A hardness	57	n.b.	61
Tensile shear Strength [ N/mm ] according to DIN EN 142932]	1.7	n.b.	2.5

VB, comparative example.

The results show that with the polymer composition P2 according to the invention, even without the addition of desiccants and silane adhesion promoters, a storage-stable moisture-curing composition FZ-1 is obtained whose properties in the fully reacted state are comparable to those of the comparative composition FZ-3 obtained with a drying agent and adhesion promoter. In contrast, the omission of the use of a drying agent and of an adhesion promoter leads to storage-unstable moisture-curing compositions FZ-2. The tensile shear strength according to DIN EN 14293 obtained with FZ-1 is far beyond the required characteristics of the soft parquet adhesive in the standard DIN EN 14293.