阅读说明：本技术 可辐射固化且可印刷的组合物 (Radiation curable and printable composition ) 是由 S·拉瑙 A·古塔克 J·克莱因 C·梅克尔-约纳斯 R·杜内凯克 M·博尼格特 于 2020-05-08 设计创作，主要内容包括：本发明涉及对基于(甲基)丙烯酸酯-和硅烷-封端的聚合物的可辐射/湿气双重固化组合物(其可用作3D印刷材料并提供各向同性和弹性体特性)的辐射。本发明进一步涉及其用作3D印刷材料的用途和使用所述组合物的印刷方法。(The present invention relates to the irradiation of radiation/moisture dual curable compositions based on (meth) acrylate-and silane-terminated polymers, which can be used as 3D printing materials and provide isotropic and elastomeric properties. The invention further relates to the use thereof as 3D printing material and to a printing method using said composition.)

1. A reaction curable printable composition comprising

a) At least one first polymer A comprising at least one terminal group of the general formula (I)

-A¹-C(＝O)-CR¹＝CH₂ (I)，

Wherein

A¹Is a divalent bonding group containing at least one heteroatom; and is

R¹Selected from H and C₁-C₄Alkyl, preferably H and methyl;

and optionally present

At least one terminal group of the formula (II)

-A²-SiXYZ (II)，

Wherein X, Y, Z are independently selected from hydroxyl and C₁To C₈Alkyl radical, C₁To C₈Alkoxy and C₁To C₈(iii) acyloxy, wherein X, Y, Z is a substituent directly bonded to a Si atom or two of substituents X, Y, Z form a ring together with the Si atom to which they are bonded, and at least one of the substituents X, Y, Z is selected from hydroxy, C₁To C₈Alkoxy and C₁To C₈An acyloxy group; and is

A²Is a divalent bonding group containing at least one heteroatom;

wherein the polymer backbone of the at least one polymer A is selected from the group consisting of polyalkylene oxides, poly (meth) acrylates, polyesters, and combinations thereof;

and optionally B) at least one second polymer B comprising at least one terminal group of the formula (II)

-A²-SiXYZ (II)，

Wherein X, Y, Z are independently selected from hydroxyl and C₁To C₈Alkyl radical, C₁To C₈Alkoxy and C₁To C₈(iii) acyloxy, wherein X, Y, Z is a substituent directly bonded to a Si atom or two of substituents X, Y, Z form a ring together with the Si atom to which they are bonded, and at least one of the substituents X, Y, Z is selected from hydroxy, C₁To C₈Alkoxy and C₁To C₈An acyloxy group;

A²is a divalent bonding group containing at least one heteroatom; and is

Wherein the polymer backbone of the at least one polymer B is optionally selected from the group consisting of polyalkylene oxides, poly (meth) acrylates, polyesters, and combinations thereof; and is

Wherein the first polymer a comprises at least one end group of formula (II) and/or the composition comprises a second polymer B.

2. The reaction-curable printable composition according to claim 1, wherein the composition is in the form of a paste and has a yield stress of more than 25, preferably 50 or more, more preferably 75 or more, wherein the yield stress can be calculated by using the following formula:

where τ is the shear stress, k_ocIs Casson yield stress, k_cIs the Casson plastic viscosity and gamma is the shear rate.

3. The reaction-curable printable composition according to claim 1 or 2, wherein the at least one polymer a

(i) Comprising at least two terminal groups of the general formula (I), or comprising at least one terminal group of the formula (I) and at least one terminal group of the formula (II); and/or

(ii) Comprising from 1 to 100 mol%, preferably from 50 to 100 mol%, of end groups of the formula (I) and from 99 to 0 mol%, preferably from 50 to 0 mol%, of end groups of the formula (II); and/or

(iii) Comprising (I) two or three, preferably two, end groups of formula (I), or (II) one end group of formula (I) and one or two, preferably one end group of formula (II), or (iii) two end groups of formula (I) and one end group of formula (II); and/or

(iv) Is a linear polymer.

4. The reaction-curable printable composition according to any one of claims 1 to 3, wherein the at least one polymer A and/or the at least one polymer B has a polyoxyethylene backbone, a polypropylene backbone or a polyoxyethylene-polyoxypropylene backbone, preferably a polyoxypropylene backbone.

5. The reaction-curable printable set according to any one of claims 1 to 4Compound (I) wherein A¹And/or A²Comprising substituted or unsubstituted ether, amide, carbamate, urethane, urea, imino, siloxane, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate groups, preferably urea and/or urethane groups.

6. The reaction-curable printable composition according to any one of claims 1 to 5, wherein in formula (I), A¹Is a radical of the formula (III)

–R¹¹-A¹¹-(R¹²-A¹²)_n-R¹³- (III)

Wherein

R¹¹、R¹²And R¹³Independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo) alkylene or arylene residue having 1 to 14 carbon atoms;

A¹¹and A¹²Each independently is selected from the group consisting of-O-C (═ O) -NH-, -NH-C (═ O) O-, -NH-C (═ O) -NH-, -NR ″ -C (═ O) -NH-, -NH-C (═ O) -NR "-, -NH-C (═ O) -, -C (═ O) -NH-, -C (═ O) -O-, -O-C (═ O) -, -O-C (═ O) -O-, -S-C (═ O) -NH-, -NH-C (═ O) -S-, -S-C (═ O) -, O-, and, -S-C (═ O) -S-, -C (═ O) -, -S-, -O-, and-NR "-wherein R" may be hydrogen or an optionally substituted hydrocarbon moiety having from 1 to 12 carbon atoms, preferably C ″₁-C₂Alkyl or hydrogen; and is

n is 0 or 1.

7. The reaction-curable printable composition according to claim 6, wherein

R¹¹Is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 4 carbon atoms;

A¹¹is a divalent radical selected from the group consisting of-O-C (═ O) -NH-, -NH-C (═ O) -NH-, and-NR ″ -C (═ O) -NH-, preferably-O-C (═ O) -NH-;

R¹³is a key or hasA divalent substituted or unsubstituted hydrocarbon residue of 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkylene residue having 1 to 8 carbon atoms;

n is 0 or 1, with the proviso that if n is 1,

then R is¹²Is a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo) alkylene residue or arylene residue having 1 to 14 carbon atoms; and is

A¹²Are divalent radicals selected from the group consisting of-NH-C (═ O) O-, -NH-C (═ O) -NH-, and-NH-C (═ O) -NR ", preferably-NH-C (═ O) O.

8. The reaction-curable printable composition according to any one of claims 1 to 7, wherein A²Is a radical of the formula (IV)

–R²¹-A²¹-(R²²-A²²)_m-R²³- (IV)

Wherein

R²¹、R²²And R²³Independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo) alkylene or arylene residue having 1 to 14 carbon atoms;

A²¹and A²²Each independently is selected from the group consisting of-O-C (═ O) -NH-, -NH-C (═ O) O-, -NH-C (═ O) -NH-, -NR ″ -C (═ O) -NH-, -NH-C (═ O) -NR "-, -NH-C (═ O) -, -C (═ O) -NH-, -C (═ O) -O-, -O-C (═ O) -, -O-C (═ O) -O-, -S-C (═ O) -NH-, -NH-C (═ O) -S-, -S-C (═ O) -, O-, and, -S-C (═ O) -S-, -C (═ O) -, -S-, -O-, and-NR "-wherein R" may be hydrogen or an optionally substituted hydrocarbon moiety having from 1 to 12 carbon atoms, preferably C ″₁-C₂Alkyl or hydrogen; and is

m is 0 or 1.

9. The reaction-curable printable composition according to claim 8, wherein

R²¹Is a bond or a divalent substituted or unsubstituted carbon atom having 1 to 20 carbon atomsPreferably an unsubstituted alkylene residue having 1 to 4 carbon atoms;

R²³is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 3 carbon atoms;

n is 0 or 1, with the proviso that if n is 0,

then A is²¹Is a divalent radical selected from the group consisting of-O-, -O-C (═ O) -NH-, -NH-C (═ O) -NH-, and-NR ″ -C (═ O) -NH-, preferably-O-, -O-C (═ O) -NH-, or-C (═ O) -NH-; and is

With the proviso that if n is 1,

then A is²¹Is a divalent radical selected from the group consisting of-O-, -O-C (═ O) -NH-, -NH-C (═ O) -NH-, and-NR ″ -C (═ O) -NH-, preferably-O-C (═ O) -NH-;

R²²is a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo) alkylene residue or arylene residue having 1 to 14 carbon atoms; and is

A²²Is a divalent radical selected from the group consisting of-NH-C (═ O) O-, -NH-C (═ O) -NH-, and-NH-C (═ O) -NR-, preferably-NH-C (═ O) -NH-.

10. The reaction-curable printable composition according to any one of claims 1 to 9, wherein

(1) In formula (II), X, Y and Z are independently from each other selected from hydroxy, methyl, ethyl, methoxy or ethoxy, wherein at least one of the substituents is hydroxy, or methoxy or ethoxy, preferably all substituents are selected from methoxy or ethoxy, more preferably methoxy; and/or

(2) R in the general formulae (III) and/or (IV)¹¹、R²¹And R²³Selected from a bond, methylene, ethylene or n-propylene.

11. The reaction-curable printable composition according to any one of claims 1 to 10, wherein the composition further comprises

c) At least one photoinitiator;

d) at least one filler; and/or

e) At least one catalyst.

12. The reaction-curable printable composition according to any one of claims 1 to 11, wherein the composition comprises, relative to the total weight of the composition

(1) From 0.01 to 90 wt.%, preferably from 0.1 to 80 wt.%, more preferably from 0.5 to 75 wt.% or from 25 to 75 wt.% of the at least one polymer a and optionally the at least one polymer B;

(2)0.01 to 5 wt%, preferably 0.1 to 4 wt%, more preferably 0.5 to 3.0 wt% of the at least one photoinitiator;

(3)0.01 to 60 wt%, preferably 0.1 to 50 wt%, more preferably 1 to 45 wt% or 10 to 45 wt% of the at least one filler; and/or

(4)0.01 to 5.0 wt% of at least one condensation catalyst.

13. The reaction-curable printable composition according to any one of claims 1 to 12, wherein the composition further comprises at least one reactive diluent/liquid filler, preferably selected from isobornyl acrylate, more preferably in an amount of 0.01 to 70 wt%.

14. Method for manufacturing a three-dimensional component by extrusion filament manufacturing, the method comprising

(a) Printing the reaction-curable printable composition according to any one of the preceding claims in a layer-by-layer manner to form the three-dimensional part;

(b) curing the printed layer of the reaction-curable printable composition to obtain the three-dimensional part,

wherein the curing step (b) optionally comprises: a first curing step comprising exposing the printed layer to radiation, preferably ultraviolet radiation; and a second curing step comprising exposing the printed layer to moisture, preferably atmospheric moisture.

15. Use of a reaction curable printable composition according to any one of claims 1 to 13 as a 3D printing material.

Examples

Example 1: (meth) acrylate-terminated polymers

TABLE 1 (all amounts are in% by weight)

DOTL: dioctyltin dilaurate

In a first step, polyol (PPG), isocyanate (IPDI) and catalyst (DOTL) were mixed at 400U/min under nitrogen at 80 ℃ for 2.5 hours. The molar ratio of OH groups to NCO groups is 1: 1. After the reaction, the reaction mixture was cooled to 25 ℃ and then acrylate was added (in an amount corresponding to a molar ratio of 1: 1 OH (polyol) to NCO: OH (acrylate)). Mix at 25 ℃ for 3 hours. The polymers 1 to 3 obtained were clear or slightly turbid (polymer 2) liquids.

Example 2: formulations

Polymers 1 to 3 of table 1 were used in various formulations. All amounts given are in weight% relative to the total weight of the composition. All formulations were tack-free after curing (curing with uv light). Hardness measurements were carried out according to DIN EN ISO 868:2003 using a durometer. The measurement of the mechanical properties (tensile test) is carried out in accordance with DIN 53504: 2017.

TABLE 2 (all amounts are in% by weight)

Example 3: 3D printing formulations based on (meth) acrylate terminated polymers

TABLE 3 (all amounts are in weight%)

Example 4: preparation of methacrylate-and silane-terminated polymers

In a first step, 72.8% by weight of polypropylene oxide (PPG 2000), 16.2% by weight of isophorone diisocyanate (IPDI) and 0.07% by weight of dioctyltin Dilaurate (DOTL) were mixed at 400U/min under nitrogen at 80 ℃ for 0.5 hour. The molar ratio of OH groups to NCO groups is 1: 2. After the reaction, the reaction mixture was cooled to 25 ℃ and then 6.5% by weight of Aminopropyltrimethoxysilane (AMMO) were added and after 0.5 hour 4.5% by weight of hydroxyethyl methacrylate (HEMA) were added (in amounts corresponding to 1: 2: 0.5: 0.48 OH (from polyol): NCO: NH)₂(from AMMO) to OH (acrylate from HEMA). Mix at 25 ℃ for 4.5 hours. Methacrylate-terminated polymers, silane-terminated polymers and mixtures of methacrylate-and silane-terminated polymers were obtained. The methacrylate-and silane-terminated polymers obtained are of molecular weight M_w7400g/mol (determined by Gel Permeation Chromatography (GPC) according to DIN 55672-1:2007-08 with Tetrahydrofuran (THF) as eluent) and a viscosity of 68000mPa.s (Anton Paar, Physica MCR 301, 23 ℃, Tan PP 25).